Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “TCO”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Developing Fuel Cell Electric Powertrain Architectures for Commercial Vehicles

Here, this article addresses the architecture development for a commercial vehicle fuel cell electric powertrain by establishing a clear multi-step formalized workflow that employs a unique technoeconomic solution for architecture selection. The power capability of the fuel cell, the energy capacity and chemistry of the electrical energy storage (battery), the DC-DC converter (including the input current rating and isolation resistance requirements), the traction drive solution, the on-board hydrogen storage solution, and the real-time power-split management of the fuel cell and the battery are all considered and developed in this effort. The methods were used to select architecture for Class 8 urban, regional, and line haul applications. When compared to traditional load-following power-split controllers, an energy management power-split controller can increase system energy efficiency by up to 19.5%. The energy-efficient power-split controller may increase the required battery capacity for an equivalent life by up to 2.6 times. The impact on the total cost of ownership (TCO) for a variety of financial cases demonstrates that high C-rate capable batteries have the potential to provide better TCO solutions over a six-year vehicle life than low C-rate capable batteries. To achieve TCO parity with the 600 A non-isolated DC-DC converter case, the specific choice of the fuel cell DC-DC converter to achieve a target power output based on current levels (from 500 A to 2400 A) shows that efficiency decreases and cost increases due to the higher current, requiring fuel cell prices to decrease by $50–$100/kW, $60–$110/kW, and $100–$220/kW for urban, regional, and line haul applications, respectively. Key recommendations for powertrain system architectures are provided, with specifics based on vehicle dynamics, mission and application characteristics, end customer use-case profile, critical powertrain component costs, and architecture selection cost function. This study rigorously demonstrates the interplay of the above parameters, with a focus on TCO, and provides application decision-makers with a mechanism and well-defined set of impact factors to consider as part of their architecture selection process.

25 ENERGY STORAGE↗
DOE OSTI2026

Total Cost of Ownership Reduction Using Passive Pre-Chamber Ignition in Natural Gas Engines

Spark plug durability is a factor affecting the total cost of ownership (TCO) of spark-ignited natural gas engines, with some heavy-duty platforms requiring plug replacement after only 750 hours of operation. The high ignition energy demand under lean or diluted conditions accelerates electrode wear, shortening plug life and increasing maintenance frequency. This work evaluates passive pre-chamber (PC) ignition operating at lowered spark energies as a strategy to reduce spark energy requirements and extend plug durability, thereby lowering TCO. Experiments were conducted on a medium-duty Cummins 6.7L ISB engine at 1600 RPM and 50% load under varying exhaust gas recirculation (EGR) dilution levels (0–40%). Two passive pre-chambers with 1.1 mm and 1.6 mm nozzle diameters were compared with conventional spark ignition (SI). SI was operated with a fixed coil dwell of 4 ms (~90 mJ), while the PC configuration was tested across 2–4 ms dwell times (~30–90 mJ). Cylinder pressure analysis revealed that PC ignition sustained stable combustion at significantly lower spark energies than SI, with improved combustion stability at ~30 mJ compared with SI at ~90 mJ. The PC system also extended the dilution tolerance beyond that achievable with SI, while delivering up to ~2% higher indicated thermal efficiency and reducing the COV by nearly 90% at 30% EGR. A TCO analysis was conducted to assess the economic benefit of adopting a passive PC system operating at reduced spark energies compared to SI. It was found that adopting a passive PC system could reduce TCO by approximately $11,000 per engine over a five-year operational period, primarily due to fuel savings, extended spark plug life, and reduced maintenance frequency. These projections were weighed against the additional hardware cost of the pre-chamber, yielding a rapid estimated return on investment of ~300 operating hours. Therefore, this work motivates continued research and development of passive PC technology and its commercial adoption in natural gas engines used in transportation applications.

Dhotre, Akash [University of Minnesota]↗
NASA NTRS2012

High Precision, Absolute Total Column Ozone Measurements from the Pandora Spectrometer System: Comparisons with Data from a Brewer Double Monochromator and Aura OMI

We present new, high precision, high temporal resolution measurements of total column ozone (TCO) amounts derived from ground-based direct-sun irradiance measurements using our recently deployed Pandora single-grating spectrometers. Pandora's small size and portability allow deployment at multiple sites within an urban air-shed and development of a ground-based monitoring network for studying small-scale atmospheric dynamics, spatial heterogeneities in trace gas distribution, local pollution conditions, photochemical processes and interdependencies of ozone and its major precursors. Results are shown for four mid- to high-latitude sites where different Pandora instruments were used. Comparisons with a well calibrated double-grating Brewer spectrometer over a period of more than a year in Greenbelt MD showed excellent agreement and a small bias of approximately 2 DU (or, 0.6%). This was constant with slant column ozone amount over the full range of observed solar zenith angles (15-80), indicating adequate Pandora stray light correction. A small (1-2%) seasonal difference was found, consistent with sensitivity studies showing that the Pandora spectral fitting TCO retrieval has a temperature dependence of 1% per 3K, with an underestimation in temperature (e.g., during summer) resulting in an underestimation of TCO. Pandora agreed well with Aura-OMI (Ozone Measuring Instrument) satellite data, with average residuals of <1% at the different sites when the OMI view was within 50 km from the Pandora location and OMI-measured cloud fraction was <0.2. The frequent and continuous measurements by Pandora revealed significant short-term (hourly) temporal changes in TCO, not possible to capture by sun-synchronous satellites, such as OMI, alone.

Ozone↗
NASA NTRSDate not supplied

The Impact of Atmospheric Dynamics and Anthropogenic Very Short-Lived Chlorine Species on the Recovery of Extra-Polar Ozone

The successful implementation of the Montreal Protocol has led to a decrease in the atmospheric abundance of ozone-depleting substances and a slowing in the destruction of the ozone layer. Previous studies have suggested that atmospheric dynamics, or a rise in compounds not regulated by the Montreal Protocol, such as very short-lived chlorine species (VSL Cl), may lead to a slower than expected recovery of the ozone layer. In this presentation, we examine the expected recovery of total column ozone (TCO) and stratospheric column ozone (SCO) to values observed in 1980 using a novel multiple linear regression (MLR) model that involves a month-by-month regression. The MLR model is trained to TCO anomalies from six data records (SBUV v8.7 MOD, SBUV v8.6 COH, WOUDC, GSG, GTO-ECV, MSR-2) over 1979 to 2021 for the Northern Hemisphere (35N – 60N), the Southern Hemisphere (60S – 35S) and the Tropics (20S – 20N), and SCO anomalies from ML-TOMCAT for these same zonal bands. The MLR includes the effect of halogens (equivalent effective stratospheric chlorine (EESC)), total solar irradiance, stratospheric aerosol optical depth, quasi-biennial oscillation, and the El Niño Southern Oscillation as regressors. We also include the effect of atmospheric dynamics such as the Brewer-Dobson Circulation, Arctic Oscillation, and the Antarctic Oscillation, and VSL Cl species in the formulation of EESC. We use a novel approach to the MLR framework, by separating the observed and regressor time series into the respective months (separating all of the Januarys, Februarys, etc.). Then we conduct a regression for each month from 1979 to 2021 for the three zonal bands denoted above. The model results for each month are combined together to achieve a full monthly time series from 1979 to 2021. We use this novel approach to ascertain the effect of atmospheric dynamics on TCO and SCO, since the dynamical proxies affect ozone in a distinctly different manner for various months. In this presentation, we will quantify the role of both the inclusion of VSL Cl species in the formulation of EESC as well as atmospheric dynamics in explaining the slower than expected recovery of extra-polar TCO and SCO over the past decade.

Laura A. McBride↗
DOE OSTI2018

Containing Tc-99 Using a Multi-sorbing Barrier Material - 18249

Immobilization of Tc-99 is a challenge at on-site waste disposal facilities in the DOE complex because the oxyanion pertechnetate (TcO{sub 4}{sup -}) binds weakly (if at all) to the surface of mineral solids and other conventional barrier materials (distribution coefficient, Kd<2 mL/g). The study described herein evaluated TcO{sub 4}{sup -} uptake from aqueous solutions using a multi-sorbing organo-clay barrier material synthesized from sodium-bentonite (Na-B) exchanged with hexadecyltrimethylammonium (HDTMA). The exchange transformed the negatively charged surface of Na-B to a positively charged surface to bind TcO{sub 4}{sup -}. Batch tests were conducted to evaluate sorption of TcO{sub 4}{sup -} onto the multi-sorbing clay barrier material using ammonium-pertechnetate solutions with activity ranging from 1000 to 2,000,000 pCi/L. Tests were conducted with a solid-to-liquid ratio of 1:100 in 50-mL centrifuge tubes rotated at 30 rpm for 24 hr. Solutions were created by dissolving ammonium-pertechnetate in DI water or synthetic low-level radioactive waste leachate. Solids were separated from the test solution by centrifugation at 4000 rpm for 10 min. A liquid scintillation counter was used to measure the Tc-99 in solution. Isotherms from the batch tests show that the multi-sorbing barrier material is very effective in removing Tc-99, with Kd > 2900 mL/g. Using this high capacity sorbent in engineered barriers may provide a sustainable solution to control release of Tc-99 and other anions of concern from on-site disposal facilities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2020

A Post-2013 Dropoff in Total Ozone at a Third of Global Ozonesonde Stations: Electrochemical Concentration Cell Instrument Artifacts?

An international effort to improve ozonesonde data quality and to reevaluate historical recordshas made significant improvements in the accuracy of global network data. However, between 2014 and2016, ozonesonde total column ozone (TCO; O3) at 14 of 37 regularly reporting stations exhibited a suddendropoff relative to satellite measurements. The ozonesonde TCO drop is 3–7% compared to satellite andground‐based TCO, and 5–10% or more compared to satellite stratospheric O3profiles, compromising theuse of recent data for trends, although they remain reliable for other uses. Hardware changes in theozonesonde instrument are likely a major factor in the O3dropoff, but no single property of the ozonesondeexplains thefindings. The bias remains in recent data. Research to understand the dropoff is in progress; thisletter is intended as a caution to users of the data. Ourfindings underscore the importance of regularozonesonde data evaluation.

ozonesonde TCO drop↗
DOE OSTI2024

Indirect Liftoff Mechanism for High‐Throughput, Single‐Source Laser Scribing for Perovskite Solar Modules

A high‐throughput, single‐source laser scribing method exploiting a transparent conducting oxide (TCO) indirect liftoff mechanism is developed to produce serially interconnected perovskite solar modules. The TCO‐based indirect liftoff mechanism relies solely on laser absorption in the front transparent electrode material reducing thermal damage to the overlying layers and allowing for fast scribing speeds with low‐cost μs‐pulse duration fiber laser systems. Minimal resistive power losses are observed with the method compared to conventional ablative laser scribes, maintaining the power conversion efficiencies of small‐area devices (≈0.2 cm 2 ) across significantly larger deposition areas (≈1 cm 2 ). Finally, demonstrating > 3 m s −1 processing speeds, TCO‐based liftoff provides the highest throughput laser scribing method for thin‐film photovoltaic devices produced on glass/TCO substrates, capable of processing large‐area perovskite solar modules at a manufacturing scale.

14 SOLAR ENERGY↗
DOE OSTI2018

The Nature of the Technetium Species Formed During the Oxidation of Technetium Dioxide with Oxygen and Water

The oxidation of TcO 2 with O 2 in the presence of H 2 O at 250 °C was investigated; Tc 2 O 7 and a red product were observed after the reaction. UV/Visible spectroscopy and a cerium titration on the “red” product are consistent with the presence of a reduced Tc species. It is proposed that the “red” product was formed by the hydrolysis of Tc 2 O 7 to HTcO 4 followed by the reduction of HTcO 4 . The reaction products of TcO 2 with O 2 /H 2 O at 250 °C were also studied by mass spectrometry. The main dinuclear species were Tc 2 O 7 and Tc 2 O 5 , while the main mononuclear species were TcO 3 and HTcO 4 . The compound HTcO 4 and associated hydrates were simulated to identify candidate structures for the “red” product; however, neither the acid nor any related hydrates exhibited the UV/Visible signature of the “red” product.

Childs, Bradley C.↗
DOE OSTI2021

High stability of flexible perovskite transparent conductive oxide film via van der Waals heteroepitaxy

Transparent conducting oxides (TCOs), such as indium-tin oxide (ITO) and indium gallium zinc oxide (IGZO), are essential components in the design of flexible optoelectronic devices. However, it is still a challenge to prepare low-cost flexible transparent conductive film for achieving the flexible functionality together with high optical transparency and electrical conductivity. Herein, fluorphlogopite (mica) is selected as the bendable and transparent substrate for the fabrication of low-cost perovskite CaVO 3 TCO epitaxial film. Benefitting from thin mica substrate with high Young’s modulus of 200 GPa, flexible CaVO 3 TCO epitaxial film exhibits high mechanical stability in terms of electrical conductivity and optical transparency after bending up to 10 5 cycles. The change of resistance can reflect the bending curvature and strain state. Finally, our results provide a new pathway to design superior mechanical flexibility and stability CaVO 3 TCO films for application in flexible, light-weight, and portable smart optoelectronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Part II: Predicting performance of $\mathrm{DOWEX 21K}$ resin for remediation of comingled contaminants in groundwater

The selectivity of ion exchange (IX) resins for aqueous contaminant removal can be impacted by changing concentrations of competing natural groundwater ions. In a two-part investigation, the Hanford Site 200 West Area pump-and-treat (P&T) facility in Washington State, USA is used as a case study to evaluate the performance of two IX resins for groundwater treatment: Purolite® A532E for pertechnetate (TcO 4 - ) removal, explored in Part I, and DOWEX 21K (DOWEX) for uranium (U) removal. In Part II, DOWEX selectivity for U, as uranyl carbonate species, and uptake kinetics is quantified in a series of laboratory-scale aqueous batch experiments containing Hanford-relevant concentrations of competing anions nitrate (NO 3 - ), sulfate (SO 4 2- ), chloride (Cl - ), and carbonate (CO 3 2- ), as well as co-mingled contaminant TcO 4 - . Here the results demonstrate that DOWEX trimethylammonium functional groups are highly selective for U carbonate species (85–100 % uptake) under all conditions investigated. Only NO 3 - concentrations of 100 mM were shown to decrease U removal, with the extent (85–99 %) depending on competing anion concentrations present in solution. However, at the highest NO 3 - concentrations reported for groundwaters treated at the P&T facility (25 mM), the effect on U uptake is minimal. The batch sorption results are modeled to obtain chloride normalized equilibrium exchange coefficients (K) for predicting DOWEX performance: K SO4--/Cl- = 2.0, K NO3-/Cl- = 5.0, K HCO3-/Cl- = 1.5, K TcO4-/Cl- = 2,000, and K U/Cl- = 50,000. These K values predict little effect of current and future influent chemistries on U removal by DOWEX, where both uranyl carbonate species and TcO 4 - are removed such that effluent concentrations meet groundwater treatment requirements.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Anion-exchanged and quaternary ammonium functionalized MIL-101-Cr metal-organic framework (MOF) for ReO 4 – /TcO 4 – sequestration from groundwater

There are few effective technologies for the sequestration of highly water-soluble pertechnetate (TcO 4 – ) from contaminated water despite the urgency of environmental and public health concerns. Here, anion exchanged and cetyltrimethylammonium bromide (CTAB) functionalized MIL-101-Cr-NO 3 were investigated for perrhenate (ReO 4 – ), a surrogate of TcO 4 – , sequestration from artificial groundwater. Cl – , I – , and CF 3 SO 3 – exchanged MIL-101-Cr proved more effective at ReO 4 – removal than the parent MIL-101-Cr-F. Compared to the parent framework, CTAB functionalized MIL-101-Cr-NO 3 increased ReO 4 – removal capacity from 39 to 139 mg/g, improved the reaction kinetics from ~30 to <10 min to reach full adsorption capacity and the selectivity for ReO 4 – over competing NO 3 – , CO 3 2– , SO 4 2– , and Cl – . Spectroscopic data indicated that the chemical speciation of Re in the exchanged MIL-101-Cr remained ReO 4 – , indicating synergistic sequestration through both anion exchange and non-ion exchange binding with the positively charged ligand of CTAB. These studies foreshadow potential applications of MOFs for the remediation of 99 TcO 4 – from contaminated environments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Accumulation mechanisms for contaminants on weak-base hybrid ion exchange resins

Mechanism of hexavalent chromium removal (Cr(VI) as CrO 4 2- ) by the weak-base ion exchange (IX) resin ResinTech® SIR-700-HP (SIR-700) from simulated groundwater is assessed in the presence of radioactive contaminants iodine-129 (as IO 3 - ), uranium (U as uranyl UO 2 2+ ), and technetium-99 (as TcO 4 - ), and common environmental anions sulfate (SO 4 2- ) and chloride (Cl-). Batch tests using the acid sulfate form of SIR-700 demonstrated Cr(VI) and U(VI) removal exceeded 97%, except in the presence of high SO 4 2- concentrations (536 mg/L) where Cr(VI) and U(VI) removal decreased to ≥ 80%. However, Cr(VI) removal notably improved with co-mingled U(VI) that complexes with SO 4 2- at the protonated amine sites. These U–SO 4 2- complexes are integral to U(VI) removal, as confirmed by the decrease in U(VI) removal (<40%) when the acid chloride form of SIR-700 was used instead. Solid phase characterization revealed that CrO 4 2- is removed by IX with SO 4 2- complexes and/or reduced to amorphous Cr(III)(OH) 3 at secondary alcohol sites. Tc(VII)O 4 - and I(V)O 3 - also undergo chemical reduction, following a similar removal mechanism. Oxyanion removal preference is determined by the anion reduction potential (CrO 4 2 - >TcO 4 - >IO 3 - ), geometry, and charge density. For these reasons, 39% and 69% of TcO 4 - and 17% and 39% of IO 3 - are removed in the presence and absence of Cr(VI), respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A techno-economic assessment of carbon dioxide removal pathways via biochemical conversion of lignocellulose to biofuels and bioplastics

Biomass carbon removal and storage (BiCRS) is a promising pathway to mitigate climate change via large scale removal of atmospheric carbon dioxide (CO 2 ). We modeled several fermentation technologies, producing a variety of bioproducts from lignocellulosic feedstocks, to understand their levelized cost of CO 2 removal under multiple scenarios. Lifecycle greenhouse gas (GHG) emissions are accounted to provide cradle-to-grave estimates of carbon intensity (CI). We did not account for the avoided fossil CO 2 emissions from the use of biofuels in our CO 2 removal cost calculations, because avoided emissions do not contribute to CO 2 removal. The main products from the fermentation technologies we modeled include renewable diesel, ethanol, sustainable aviation fuel (SAF), and polyethylene (PE), with co-products including CO 2 , adipic acid, steam, and electricity. PE, depending on its end-of-life management, can serve as a form of biogenic carbon storage. PE has the potential to remove 1.2–1.5 tCO 2 per dry t-biomass, whereas biofuels have the potential to remove 0.3–0.9 tCO 2 per dry t-biomass, indicating that PE production is a more efficient method of carbon removal. We quantify costs of CO 2 removal to be $\$$60 – $\$$675 per metric tCO 2 removed across the various fermentation pathways. Under the scenarios analyzed, bioplastic production from lignocellulosic biomass is a more cost-effective route to CO 2 removal than biofuel production, with costs of CO 2 removal via bioplastics being 50–90 % lower than that of biofuels. Future research should explore the potential benefits and drawbacks of expanding bioplastic production for large-scale CO 2 removal.

09 BIOMASS FUELS↗
DOE OSTI2015

Degradation of transparent conductive oxides: Interfacial engineering and mechanistic insights

Transparent conductive oxides (TCOs) are a known failure mode in a variety of thin film photovoltaic (PV) devices, through mechanisms such as resistivity increase and delamination. Degradation science studies of these materials, as well as most PV systems, have primarily utilized industry standard qualification protocols, which are not designed to be used as lifetime prediction tests. Here, this work applies a data science approach to this engineering challenge, utilizing commercially available TCOs and subjecting them to an array of stressors, including environmental and material stressors. Optical, electrical and surface sensitive TCO property metrics were monitored and analyzed en mass. Different degradation mechanisms and modes were observed when different stressor combinations were applied; TCO surfaces are sensitive to the proportion of water and light in an exposure, yellowing of the TCO only occurs when humidity and UV light are combined, and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)) application results in hazing and roughening of aluminum-doped zinc oxide (AZO). Using multi-variate analytics and plotting critical material properties against one another in a mechanistic plot, trade-offs between properties and the activation of different degradation mechanisms become readily apparent. In addition to a survey of failure modes of TCOs, a possible solution to the degradation of AZO was examined: the application of an organofunctional silane layer. The application of a thin APTES (3-aminopropyltriethoxysilane) film nearly eliminated the observed edge effects and greatly reduced the resistivity increase caused by damp heat exposure of AZO.

14 SOLAR ENERGY↗
DOE OSTI2021

Ultrastable Zirconium-Based Cationic Metal–Organic Frameworks for Perrhenate Removal from Wastewater

The effective removal of radioactive 99 TcO 4 – anion from nuclear wastewater remains a very difficult unsolved problem. Functional adsorbent materials with high stability, anion-exchange capacity, excellent selectivity, and recyclability are much needed to solve this problem. In this work, we designed two stable cationic metal–organic frameworks (MOFs)—Zr-tcbp-Me and Zr-tcpp-Me—for possible use as adsorbent materials to remove 99 TcO 4 – . Both compounds were synthesized by solvothermal reactions of the tetracarboxylate ligand with zirconium salt, followed by postsynthetic modification (N-methylation). Here, the crystallinity of both zirconium-based MOFs can be well retained under harsh conditions, and they exhibit high adsorption capacity and selectivity toward ReO 4 – anion, a nonradioactive analogue of 99 TcO 4 – . Zr-tcbp-Me and Zr-tcpp-Me demonstrate the highest framework stability toward acidity among all previously reported cationic MOFs that have been tested for perrhenate removal from wastewater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies

Here, ditechnetium heptoxide was synthesized from the oxidation of TcO 2 with O 2 at 450 °C and characterized by single crystal X-ray diffraction (SCXRD), electron impact mass spectrometry (EI-MS) and theoretical methods. Refinement of the structure at 100 K indicates that Tc 2 O 7 crystallizes as a molecular solid in the orthorhombic space group Pbca (a = 7.312(3) Å, b = 5.562(2) Å, c = 13.707(5) Å, V = 557.5(3) Å 3 ). The Tc 2 O 7 molecule can be described as corner-sharing TcO4 tetrahedra (Tc---Tc = 3.698(1) Å and Tc-O Bri -Tc = 180.0°). The EI-MS spectrum of Tc 2 O 7 consists of both mononuclear and dinuclear species. The main dinuclear species in the gas-phase are Tc 2 O 7 (100%) and Tc 2 O 5 (56%), while the main mononuclear species are TcO 3 (33.9%) and TcO 2 (42.8%). The difference in the relative intensities of the M 2 O 5 (M = Tc, Re) fragments (1.7% for Re) indicate that these Group 7 elements exhibit different gas phase chemistry. The solid-state structure of Tc 2 O 7 was investigated by density functional theory (DFT) methods. The optimized structure of the Tc 2 O 7 molecule is in good agreement with the experimental one. Simulations indicate that the more favorable geometry for the Tc 2 O 7 molecule in the gas-phase is bent (Tc-O Bri -Tc = 156.5°), while linear (Tc-O Bri -Tc = 180.0°) is favored in the solid state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Focused Ion Beam-Scanning Transmission Electron Microscopy with Energy-Dispersive X-ray Spectroscopy Study on Technetium Incorporation within Iron Oxides through Fe(OH) 2 (s) Mineral Transformation

Incorporation of Tc(IV) into iron oxide/hydroxide minerals has been explored and proposed as a promising pathway to preventing Tc(IV) reoxidation to environmentally mobile pertechnetate (TcO 4 - ) and improving long-term immobilization of radioactive technetium-99 (Tc). However, visual evidence evaluating the distribution of Tc(IV) incorporated within iron oxide/hydroxide phases has not been available, until now, despite potential implications on Tc(IV) stability within the host phase. For the purpose of this study Tc(IV) incorporation into iron oxide/hydroxide phases was facilitated via Fe(OH) 2 (s) oxidation and mineral transformation to magnetite (Fe 3 O 4 ). Focused ion beam - scanning transmission electron microscopy equipped with energy-dispersive X-ray spectroscopy (FIB/STEM-EDS) methods were then combined with X-ray diffraction and absorption spectroscopy techniques to characterize and visually demonstrate that, for the first time, Tc(IV) is heterogeneously incorporated into different iron oxide/hydroxide phases as Tc(IV)-incorporated magnetite and/or TcO 2 ·2H 2 O(s) via different incorporation mechanisms. Heterogeneous distribution of Tc(IV) in magnetite suggests either (i) TcO4- is reduced quickly at the magnetite surface and then encapsulated into magnetite during continued octahedral crystal growth, or (ii) Tc(IV) alternatively partitioned into multiple layers of a blocky, plate-like morphological magnetite structure showing stratified Tc. With limited Tc-hematite (Fe 2 O 3 ) incorporation, the results suggest that TcO 2 ·2H 2 O(s) is formed and mainly associated/embedded in fibrous nanometer-sized polycrystalline hematite. This work highlights the power of modern state-of-the-art FIB/STEM-EDS approach to provide essential visual insights of the Tc-iron oxide/hydroxide incorporation and generate reliable mechanism-informed designs for waste forms relying on Tc mineral incorporation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗