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DOE OSTI2025

Phosphate-modulated transformation of Sb(V)-bearing ferrihydrite under microbial iron- and sulfate-reducing conditions

Antimony (Sb) is a toxic metalloid that poses environmental risks in terrestrial and aquatic systems. The fate of the Sb(V) oxyanion, Sb(OH) 6 − , is governed by complex biogeochemical processes, including immobilization by ferric (Fe(III)) oxides, reduction by sulfide, and the less-explored competitive adsorption with other anions such as phosphate (PO 4 3− ). Here, this study investigates the interplay between such mechanisms in controlling the behavior of Sb(V) associated with ferrihydrite (Fh) under Fe(III)- and sulfate-reducing conditions, with a particular emphasis on the role of phosphate in influencing Sb(V) mobility and transformation. Anoxic reactors that contained Sb(V)-coprecipitated Fh, varying PO 4 3− concentrations (0, 0.2, and 2 mM), and sulfate, were inoculated with a microbial community sourced from Sb-contaminated soil. Additionally, abiotic reactors with either Sb(V)-adsorbed or Sb(V)-coprecipitated Fh and different PO 4 3− loadings (0–100 mM) were created to investigate the competitive adsorption mechanisms in the absence of microbial activity. Results from the abiotic reactors suggest that Sb(V) is likely incorporated into the Fh structure, with only minor amounts remaining surface-bound and extractable by PO 4 3− . In the biotic reactors, microbial Fe(III) and sulfate reduction were more extensive in the presence of PO 4 3− . At 0.2 mM PO 4 3− , microbial activity transformed Fh into siderite and led to the complete reduction of Sb(V) to Sb(III) as stibnite (Sb 2 S 3 ). At 2 mM PO 4 3− , the greater coverage by PO 4 3− stabilized Fh and decreased the extent of both Fe(III) and Sb(V) reduction, and shifted the reduced products to mackinawite and Sb(III) adsorbed onto Fh, in addition to stibnite formation. This study demonstrates that while PO 4 3− may not directly compete with Sb(V) for sorption sites, it can influence Sb mobility in Fe(III)- and sulfate-reducing environments by enhancing microbial activity and altering the mineralization pathways.

Microbial Fe(III) and sulfate reduction↗

DOE OSTI2017

A low-temperature synthetic route to ternary iron-manganese metal fluorides nanoparticles

Ternary metal fluoride Fe{sub x}Mn{sub 1−x}F{sub 2} (x = 0.00, 0.25, 0.50, 0.75, and 1.00), which is a potential cathode material for next-generation Li-ion batteries, were synthesized via a convenient, low-temperature, bottom-up solution-phase method. The lattice dimensions deduced from X-ray diffraction suggested formation of homogeneous solid solutions. With increasing Fe content, the morphology of the solid changed from cubic particles to dendritic, with an average particle size of 20–40 nm. The results suggested that this synthetic method constitutes a translatable route to large-scale production of ternary metal fluoride nanoparticles. - Graphical abstract: Homogeneous random solid solutions of ternary metal fluoride Fe{sub x}Mn{sub 1−x}F{sub 2} can be prepared by room temperature coprecipitation of precursors followed by drying and calcination at 350 °C. Display Omitted - Highlights: • Homogeneous ternary mixed metal iron-manganese fluoride Fe{sub x}Mn{sub 1−x}F{sub 2} nanoparticles prepared by room temperature coprecipitation and calcination. • Fe{sub x}Mn{sub 1−x}F{sub 2} nanoparticles form different morphology aggregates depending on the composition. • Lattice dimensions from X-ray diffraction suggested formation of homogeneous solid solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Synthesis of g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} heterojunction with enhanced photocatalytic performance

Graphical abstract: g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} heterojunction photocatalyst with visible-light response was prepared by a facile coprecipitation method. The results show that g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} possesses a much higher activity for the decomposition of RhB than that of the pure Ag{sub 3}PO{sub 4} particles. The most mechanism is that g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} heterojunction photocatalyst can efficiently separate the photogenerated electron–hole pairs, enhancing the photocatalytic activity of g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} composites. - Highlights: • g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} heterojunction showed much higher activity than that of Ag{sub 3}PO{sub 4}. • The high activity could be attributed to g-C{sub 3}N{sub 4} for modifying Ag{sub 3}PO{sub 4}. • More ·OH radicals may be significant reason to improve Ag{sub 3}PO{sub 4} activity. - Abstract: g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} heterojunction photocatalyst with visible-light response was prepared by a facile coprecipitation method. The photocatalysts were characterized by X-ray powder diffraction, transmission electron microscopy, UV–vis absorption spectroscopy and Fourier transform infrared spectroscopy. The photocatalytic activities of the obtained samples were tested by using Rhodamine B (RhB) as the degradation target under visible light irradiation. g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} decomposed RhB more effectively than the pure Ag{sub 3}PO{sub 4} particles did, and 2 wt.% g-C{sub 3}N{sub 4} had the highest activity. Furthermore, 2 wt.% g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} degraded high-concentration RhB more potently than unmodified Ag{sub 3}PO{sub 4} did, probably because g-C{sub 3}N{sub 4}/Ag{sub 3}PO{sub 4} heterojunction photocatalyst enhanced the photocatalytic activity by efficiently separating the photogenerated electron–hole pairs.

36 MATERIALS SCIENCE↗

DOE OSTI2014

Improvement of catalytic activity in selective oxidation of styrene with H{sub 2}O{sub 2} over spinel Mg–Cu ferrite hollow spheres in water

Graphical abstract: Uniform spinel Mg–Cu ferrite hollow spheres were prepared using carbon spheres as templates. Solid spinel Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} ferrite nanocrystals were also prepared by sol–gel auto-combustion, hydrothermal and coprecipitation methods for comparison. The samples were found to be efficient catalysts for oxidation of styrene using hydrogen peroxide as oxidant. Especially, in the case of Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} hollow spheres, obvious improvement on catalytic activity was observed and 21.2% of styrene conversion and 75.2% of selectivity for benzaldehyde were obtained at 80 °C for 6 h reaction in water. The catalyst can be magnetically separated easily for reuse and no obvious loss of activity was observed when reused in six consecutive runs. - Highlights: • Uniform spinel ferrite hollow spheres were prepared by a simple method. • The catalyst has been proved much more efficient for styrene oxidation than the reported analogues. • The catalyst can be easily separated by external magnetic field and has exhibited excellent reusability. • The catalytic system is environmentally friendly. - Abstract: Uniform spinel Mg–Cu ferrite hollow spheres were prepared using carbon spheres as templates. For comparison, solid Mg–Cu ferrite nanocrystals were also prepared by sol–gel auto-combustion, hydrothermal and coprecipitation methods. All the samples were characterized by Fourier transform infrared spectrophotometry (FT-IR), X-ray diffractometry (XRD), transmission electron microscopy (TEM) and N{sub 2} physisorption. The samples were found to be efficient catalysts for oxidation of styrene using hydrogen peroxide as oxidant. Especially, in the case of Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} hollow spheres, obvious improvement on catalytic activity was observed, and 21.2% of styrene conversion and 75.2% of selectivity for benzaldehyde were obtained at 80 °C for 6 h reaction in water. The catalyst can be magnetically separated easily for reuse and no obvious loss of activity was observed when reused in six consecutive runs.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Facile synthesis and temperature-dependent luminescence of single-phase dual-emitting CdTe@NaNO{sub 3} composite

Graphical abstract: Single-phase dual-emitting CdTe@NaNO{sub 3} composite was prepared by a facile and efficient aqueous ethanol phase assisted coprecipitation method. Its use in self-referencing luminescent thermometry was tested, by exploiting the temperature-dependence of fluorescence intensity ratio (green/red) in range of 273–473 K. - Highlights: • Single-phase green and red dual-emitting CdTe@NaNO{sub 3} composite was prepared. • CdTe QDs embedded in NaNO{sub 3} matrices exhibit photoluminescence quantum yields of 35%. • Temperature-dependent luminescent properties of CdTe@NaNO{sub 3} composite were studied. • It could be a good candidate for ratiometric temperature sensing with a high relative sensitivity. - Abstract: Single-phase dual-emitting CdTe@NaNO{sub 3} composite was prepared by a facile and efficient aqueous ethanol phase assisted coprecipitation method, providing a new type of solid-state luminescent material with processability, robustness and high luminescence. Cubic-shape Green + Red (G + R) CdTe@NaNO{sub 3} composite particles display single-excitation, dual-emission with two well-resolved, intensity-comparable fluorescence peaks. Its application potential in ratiometric luminescent thermometry was tested, by exploiting the temperature-dependence of fluorescence intensity ratio (green/red) in range of 273–473 K, and the maximum sensitivity is found to be 0.6183% K{sup −1} at 473 K. The results indicate that dual-emitting G + R CdTe@NaNO{sub 3} composite could be considered as potential candidates for ratiometric temperature sensing.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Effect of Synthetic Method and Annealing Temperature on the Structure of Hollandite-Type Oxides

Hollandite is a class of metal oxide material with the general formula A 2 B 8 O 16 . Several methods have been used in the synthesis of this type of metal oxide, and the synthetic methods reported have typically employed high annealing temperatures between 1200 and 1300 °C. Appropriate synthetic methods must be employed to successfully synthesize these hollandite-type oxides at lower annealing temperatures. Hollandite compounds have been synthesized using ceramic (high annealing temperature only) and coprecipitation (high and low annealing temperatures) methods. Annealing temperatures ranging from 1200 to 700 °C have been employed in the thermal treatment process. In this work, powder X-ray diffraction and X-ray absorption near-edge spectroscopy (XANES) were conducted on hollandite-type oxides (Ba x Al 2 x Ti 8–2 x O 16–δ ; x = 1.2; and Ba x Al x Fe x Ti 8–2 x O 16–δ, Ba x Fe 2 x Ti 8–2 x O 16–δ ; x = 1.16). Structural comparisons between materials annealed in the temperature range from 1200 to 800 °C were made, and an examination of the XANES spectra and powder X-ray diffraction patterns has provided confirmation of the absence of significant structural changes in these hollandite materials. This study has shown that hollandite-type materials can be formed using annealing temperatures as low as 700–800 °C when a coprecipitation method is used, with little change to the local and long-range structures being detected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Carbonation and Sulfidation of Mg- and Ni-Containing Solutions: Implications for Carbon Mineralization and Critical Element Recovery

Carbonation of alkaline earth metals ( e.g. , magnesium (Mg)) and sulfidation of nickel (Ni) are promising methods to achieve concurrent carbon mineralization and selective Ni recovery. However, the coexistence of alkaline earth metals and Ni from silicate ores or mining wastewater complicates the carbonation and sulfidation owing to cation coprecipitation. To better understand simultaneous metal carbonation and Ni-sulfide formation, we used Mg- and Ni-containing solutions and systematically investigated the Mg and Ni coprecipitates’ phase transformation during sequential/concurrent carbonation and sulfidation. During a single carbonation process, hydromagnesite dehydrated and formed magnesite over time. Nickel bicarbonate formed and became a Mg–Ni carbonate solid solution because of their similar ionic radii. During a single sulfidation process, the pH did not affect Ni-sulfide formation, but it controlled Mg behavior. Specifically, at pH 9.6, brucite formed, while at pH 7.8, Mg 2+ remained in the solution. For the sequential carbonation–sulfidation process, Ni-carbonate formed during carbonation converted to Ni-sulfide because of the low Ni-sulfide K sp . For the sulfidation–carbonation process, Ni-sulfide remained the same even after carbonation and Mg-carbonate precipitates. For the concurrent carbonation and sulfidation process, Mg-carbonate and Ni-sulfide formed simultaneously. Finally, this study develops a scientific foundation of carbonation and sulfidation processes, benefiting coupled CO 2 storage and sulfide-enabled resource recovery.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Impact of Synthetic Parameters on Structure and Electrochemistry of High-Entropy Layered Oxide LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2

Here, this study explored a high-entropy layered oxide (HELO), LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2 , prepared by coprecipitation followed by heat treatment. Coprecipitation yielded a kinetically favored product, and the subsequent heat treatment under various temperatures and times allowed tuning the material toward more thermodynamically favored structures. Refinement of X-ray powder diffraction (XRD) revealed that after 450 °C treatment, ~12% of the Ni 2+ in the structure was located within the lithium cation layer. After heat treatment at 600, 700, and 800 °C, there was a continued decrease of Ni 2+ in the lithium cation layer to 9.3, 6.3, and 3.7%, respectively. Longer heat treatment times at 800 °C decreased the level to 2.5%. Electrochemical behavior was evaluated by cyclic voltammetry, galvanostatic cycling, rate capability testing, and electrochemical impedance spectroscopy, where increased loaded voltage, functional capacity, rate capability, and decreased impedance were observed for samples treated at higher temperatures with lower cation mixing. X-ray absorption near edge spectroscopy (XANES) data indicated that the redox activity of Ni and Co was dominant in the electrochemistry, while the participation of Mn or Fe was minimal. The level of Ni oxidation state change between charge and discharge related to the heat treatment temperature where the samples with high cation mixing showed lower capacity consistent with some Ni 3+ in the transition metal layer inaccessible for electron transfer. Longer heat treatment times at 800 °C did not continue to provide a benefit in electrochemical function even with some additional reduction in cation mixing.

25 ENERGY STORAGE↗

DOE OSTI2026

Synthesis of NiRu-Layered Double Hydroxide for Enhanced Oxygen Evolution Reaction

Nickel−ruthenium layered double hydroxide (NiRu-LDH) was synthesized by coprecipitation using formamide as both solvent and intercalant. The synthesis was performed at various temperatures to study the impact of temperature on electrochemical performance. Temperature plays a vital role in optimizing LDH synthesis to enhance oxygen evolution reaction (OER) efficiency. The optimal temperature yielded a well-defined morphology with balanced crystallinity, leading to more active sites and improved charge transfer. Electrochemical tests indicated that the NiRu-LDH sample prepared at 50 °C (NiRu-LDH-50) required only 280 mV overpotential versus the reversible hydrogen electrode to achieve 10 mA/cm 2 and exhibited a low Tafel slope of 52 mV/dec, demonstrating excellent catalytic kinetics. This study presents the synthesis of NiRu-LDH via coprecipitation and emphasizes how reaction temperature influences LDH structural properties and OER performance.

Catalysts↗

DOE OSTI2016

Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2 -edge XANES spectroscopy

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2 -edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Synthesis of greigite (Fe 3 S 4 ) particles via a hydrothermal method

Greigite (Fe 3 S 4 ) particles, with strong ferrimagnetic behavior, have been found to have desirable uses in the areas of biomedical and environmental applications. Size-dependent magnetic properties of greigite can play a crucial role in efficiency of its applications. This study reviews two synthetic approaches to producing such particles. The methods tested within this study include a coprecipitation synthesis and a hydrothermal process. While the coprecipitation method proved to be ineffective at producing greigite, the hydrothermal process showed promise after consistently producing greigite. For the hydrothermal process, the effects of synthesis time, autoclave atmosphere, and polyvinylpyrrolidone (PVP) addition as a capping agent to control particle growth were investigated using X-ray diffractometry (XRD) with Rietveld refinement, vibrating sample magnetometry (VSM), and scanning electron microscopy (SEM). The results show that, while pyrite (FeS2) forms as an impurity phase, increasing the synthesis time up to 18 hours increases the greigite fraction up to 70 wt% and saturation magnetization up to ~ 35 emu/g for the powder synthesized in argon. The SEM micrographs of this sample reveal a mean greigite particle size of ~ 700 nm. It was found that adding PVP brings about a much more uniform microstructure of agglomerated plate-shape particles with nano-sized features.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Technetium (VII) Co-precipitation with Framework Aluminosilicates

Technetium-99 (99Tc), a long-lived radionuclide, is one of the most widespread contaminants within the Hanford subsurface. At some depths, it is only extractable with strong acids, suggesting incorporation into a solid phase. We hypothesized that Tc may have coprecipitated with feldspathoid aluminosilicates under waste tanks that had leaked caustic solutions into the vadose zone. Our objectives were to determine if Tc could be incorporated into the feldspathoids cancrinite and sodalite and under what conditions coprecipitation could occur. Our hypothesis was that sodalite was more likely to incorporate and retain Tc. Our approach was to use known methods of feldspathoid formation in solutions resembling those in Hanford waste tanks contacting sediments in terms of major ion (Na, NO3, OH, Al(OH)4, and Si(OH)4 concentrations. In some cases, Al and Si were supplied from zeolite. We used perrhenate (ReO4) as a surrogate for pertechnetate (TcO4) to avoid the radioactivity. The major findings of this study were 1) ReO4 could be incorporated into either sodalite or cancrinite but the concentration in the solid was < 1% of the competing ion Cl, NO3, or NO2. 2) The small amount of ReO4 incorporated was not exchangeable with NO3 or NO2. 3) In sodalite, NO3 was highly preferred over ReO4 but significant Re-sodalite was formed when the mole fraction in solution (Re/Re+N) exceeded 0.8. 4) A nonlinear relation between the unit cell parameter and amount of Re incorporated suggested that a separate Re-sodalite phase was formed rather than a solid solution. 5) We determined that sodalite preference for sodalite in the presence of different anions increased with the ionic size of the competing anion: Cl < CO3 < NO3 < SO4 < MnO4 < WO4 and significant incorporation did not occur unless the difference in anion radii was less than 12%. 6) Re(VII) was not significantly reduced to Re(IV) under the conditions of this experiment and Re appeared to be a good surrogate for Tc under oxidizing conditions as both oxyanions have the same size. In conclusion, incorporation of TcO4 is unlikely in the close proximity to the tanks where sodalite is likely to form in the presence of high NO3 and other anions much smaller than TcO4.

58 GEOSCIENCES↗

DOE OSTI2019

M4SF-19LL010302042: Pu Incorporation into Reduced Iron Oxide Phases

The research is focused on actinide and radionuclide sequestration in steel corrosion products. The effort described herein was focused on identifying synthesis methods for reduced Fe-oxide phases and performing Pu sorption and coprecipitation experiments to determine the fractionation of Pu into and onto these phases. Specifically, we are: Quantifying the rate of Pu incorporation to magnetite and green rust, and Characterizing the nature and morphology of sorbed and coprecipitated Pu on these phases.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2020

M4SF-20LL010302042: Process Model for Radionuclide Incorporation into Corrosion Products

This progress report (Level 4 Milestone Number M4SF-20LL010302042) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-20LL010302041. The research is focused on actinide and radionuclide sequestration in steel corrosion products. Fuel matrix degradation models suggest that the near field is likely to be reducing at the time of canister breaching, steel corrosion, and radionuclide release, but more oxidizing conditions may prevail in the far field. The incorporation of radionuclides into corrosion phases may limit the rate of radionuclide release by sequestering a portion of the radionuclide source term. For these reasons there is a need to evaluate the incorporation of Pu and other radionuclides into various Fe-oxide phases, and to understand the behavior of coprecipitated phases during mineral recrystallization processes and during re-oxidation events. Radionuclide coprecipitation with Fe minerals may impact long-term repository performance and is an ongoing research focus at Lawrence Livermore National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Steel Corrosion Impacts on Radionuclide Immobilization

This progress report (Level 4 Milestone Number M4SF-21LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-21LL01030205. The research is focused on actinide and radionuclide sequestration in steel corrosion products. Fuel matrix degradation models suggest that the near field is likely to be reducing at the time of canister breaching, steel corrosion, and radionuclide release, but more oxidizing conditions may prevail in the far field. The incorporation of radionuclides into corrosion phases may limit the rate of radionuclide release by sequestering a portion of the radionuclide source term. For these reasons there is a need to evaluate the incorporation of Pu and other radionuclides into various Fe-oxide phases, and to understand the behavior of coprecipitated phases during mineral recrystallization processes and during re-oxidation events. Radionuclide coprecipitation with Fe minerals may impact long-term repository performance and is an ongoing research focus at Lawrence Livermore National Laboratory.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Radionuclide Interaction with Hydrothermally Altered Repository Materials (M4SF-23LL010302052)

This progress report (Level 4 Milestone Number M4SF-23LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-23LL01030205. The research is focused on actinide and radionuclide sequestration in hydrothermally altered repository materials. In FY23, a manuscript was in preparation for publication summarizing our analysis of radionuclide sorption and coprecipitation into Fe oxide phases and evaluation of radionuclide partitioning values across a range of radionuclides relevant to performance assessment. We demonstrated our approach in detail using Se sorption and coprecipitation with iron oxide minerals. These data were presented in our FY22 annual report and will not be repeated here. We also initiated experiments to identify radionuclide interaction with hydrothermally altered crystalline repository and backfill materials. Recent research performed at Los Alamos National Laboratory (LANL) and Sandia National Laboratory (SNL) has provided key insights regarding the hydrothermal alteration behavior of bentonite backfill in the presence of repository materials (steel, concrete, etc.). We are now examining how mineral alteration affects retardation behavior of plutonium and a suite of other radionuclides. These experiments also allow us to test the predictive ability of our component additivity approach to surface complexation and ion exchange. Our guiding hypothesis is that a robust surface complexation/ion exchange model and associated database, developed using our L-SCIE approach, can effectively predict changes in radionuclide sorption behavior resulting from the hydrothermal alteration of mineralogy in a repository near field. A short update of results to date is presented below. A manuscript was also in preparation describing a self-consistent model and approach to simulating Se(IV) and Se(VI) sorption to 5 iron oxide phases based on our L-SCIE community database. This will be the first implementation of a multi-mineral and multi-oxidation state sorption model using our new L-SCIE database and workflow. A short summary of these results is presented below.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2024

M3SF-24LL010302052-Comprehensive Analysis of Radionuclide Interaction with Hydrothermally Altered Repository Materials

This progress report (Level 3 Milestone Number M3SF-24LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Work Package Number SF-24LL01030205. The research is focused on actinide and radionuclide sequestration in hydrothermally altered repository materials. In FY24, we completed a rigorous analysis of Se sorption to iron oxide phases using our L-SCIE sorption database. This effort explicitly accounts for surface titration behavior of oxide surfaces that was the subject of a recently published manuscript (Han et al., 2023). With this in mind, our Se sorption analysis now yields a more robust workflow for developing self-consistent surface complexation modeling approaches that can be adapted to specific SCM conceptual and numerical approaches (i.e. non-electrostatic, diffuse layer, triple layer models). In late FY24, we plan to publish the results of our comprehensive surface complexation modeling of Se(IV) and Se(VI) sorption to iron oxide mineral phases and provide a path forward to developing robust radionuclide sorption models for use in performance assessment. In FY24, we also submitted a manuscript summarizing our approach to integrating radionuclide sorption and coprecipitation phenomena and evaluation of radionuclide partitioning values across a range of radionuclides relevant to performance assessment. We demonstrated our approach in detail using Se sorption and coprecipitation with iron oxide minerals as a test case. This manuscript was recently accepted for publication in Applied Geochemistry (Balboni et al., Accepted). We also continued experiments to identify radionuclide interaction with hydrothermally altered crystalline repository and backfill materials. Recent research performed at Los Alamos National Laboratory (LANL) and Sandia National Laboratory (SNL) has provided key insights regarding the hydrothermal alteration behavior of bentonite backfill in the presence of repository materials (steel, concrete, etc.). We are now examining how mineral alteration affects retardation behavior of a suite of radionuclides of interest to repository performance assessment. These experiments also allow us to test the predictive ability of our component additivity approach to surface complexation and ion exchange. Our guiding hypothesis is that a robust surface complexation/ion exchange model and associated database, developed using our L-SCIE approach, can effectively predict changes in radionuclide sorption behavior resulting from the hydrothermal alteration of mineralogy in a repository near field. A short update of results to date is presented below.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2014

CaCO 3 Precipitation, Transport and Sensing in Porous Media with In Situ Generation of Reactants

Ureolytically driven calcite precipitation is a promising approach for inducing subsurface mineral precipitation, but engineered application requires the ability to control and predict precipitate distribution. To study the coupling between reactant transport and precipitate distribution, columns with defined zones of immobilized urease were used to examine the distribution of calcium carbonate precipitation along the flow path, at two different initial flow rates. As expected, with slower flow precipitate was concentrated toward the upstream end of the enzyme zone and with higher flow the solid was more uniformly distributed over the enzyme zone. Under constant hydraulic head conditions the flow rate decreased as precipitates decreased porosity and permeability. The hydrolysis/precipitation zone was expected to become compressed in the upstream direction. However, apparent reductions in the urea hydrolysis rate and changes in the distribution of enzyme activity, possibly due to CaCO 3 precipitate hindering urea transport to the enzyme, or enzyme mobilization, mitigated reaction zone compression. Co-injected strontium was expected to be sequestered by coprecipitation with CaCO 3 , but the results suggested that coprecipitation was not an effective sequestration mechanism in this system. In addition, spectral induced polarization (SIP) was used to monitor the spatial and temporal evolution of the reaction zone.

54 ENVIRONMENTAL SCIENCES↗