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At least 505 records · Page 28

Mechanochemical synthesis of hydraulically reactive calcium silicate minerals via thermally-assisted mechanical grinding

This study explores a thermally assisted mechanochemical approach alternative to conventional cement synthesis as a potential to produce hydraulically reactive calcium silicate phases. Ball milling of mixed CaO/SiO 2 feedstocks at temperature ranges 100-300 °C increases the formation of the Ca-O-Si bonds and precursor reactivity. Spectroscopic analyses (FTIR, MAS-NMR, UV-Vis DRS) indicate increasing amorphization with milling temperature, attributed to improved mixing and thermally assisted diffusion. Upon hydration, all treated samples exhibit exothermic heat release, with the sample prepared at 300 °C showing the most pronounced reactivity. Thermal analysis reveals weight loss consistent with C-S-H formation, confirming cement-like behavior. In summary, moderate thermal input during milling promotes structural activation and enhances downstream hydraulic reactivity, providing a proof-of-concept for energy-reduced cement precursor processing.

Alite↗

Shifting modes of iron sulfidization at the onset of OAE-2 drive regional shifts in pyrite δ 34 S records

We report total reduced inorganic S isotope ratios (δ 34 S CRS ) shift toward more negative values across much of the southern North Atlantic just before the onset of the Cenomanian-Turonian Ocean Anoxic Event (OAE-2). At the same time, there is no parallel isotopic change in the significantly larger pool of kerogen (organic) S, which indicates that the distribution and S-isotope composition of sulfide in the environment likely did not drive the change in δ 34 S CRS . Here, we investigate possible explanations for the negative shift in δ 34 S CRS values and their divergence from organic S by isolating iron sulfides for morphological identification and grain-specific isotopic analysis using secondary ion mass spectrometry (SIMS). In pre- and syn-OAE-2 sedimentary rocks from Demerara Rise, we find four distinct morphologies of iron sulfides: pyrite framboids (1–20 μm diameter), irregular pyrite aggregates (1–38 μm diameter), large cemented pyrite aggregates (~60 μm diameter), and irregular and cemented aggregates of the pyrite polymorph marcasite (1–45 μm diameter). These different textural groups have distinct S-isotopic compositions that are largely consistent through the onset of OAE-2. As such, the secular change in bulk δ 34 S CRS values likely reflects the changing proportions of these phases stratigraphically across OAE-2. All textural groups feature resolvable intra-grain δ 34 S variability, suggesting that the environments in which they formed were characterized by dynamic sulfide δ 34 S values and/or by partial closed-system distillation. We use grain-specific δ 34 S distributions to rule out shoaling of the chemocline within the sediments as a mechanism for the observed decrease in δ 34 S CRS . Instead, we propose that changes in the reactivity of the iron species delivered to Demerara Rise over the ~200 kyr leading up to the onset of OAE-2 impacted the relative contributions of pyrite with S-isotope signatures reflecting the water column, shallow sediments, and deeper sediments to the bulk sedimentary δ 34 S CRS value. Specifically, the change in iron reactivity at the onset of OAE-2 favored the production of 34 S-depleted large, cemented aggregates and framboids at the expense of more 34 S-enriched irregular aggregates. Our results underscore that bulk δ 34 S CRS measurements integrate multiple reduced phases that form via distinct reaction mechanisms and potentially in different parts of the depositional environment. Grain-specific SIMS analyses dramatically enrich our ability to interpret pyrite isotopic patterns in the geologic record.

58 GEOSCIENCES↗

Experimental characterization and potential energy savings of insulated cladding for U.S. residential buildings

This study evaluates a novel insulated cladding composed of foamed cement and vinyl siding that is designed as a retrofit product to enhance thermal performance in U.S. residential buildings. Experimental measurements showed that foamed cement exhibits a thermal conductivity of 0.0334–0.0365 W/m-K (R-value of 4.0–4.3 °F⋅ft 2 ⋅h/BTU), which is significantly higher than that of conventional fiber cement boards. Although mechanical testing confirmed the material’s brittleness and low strength, it also indicated its suitability for nonstructural insulation applications. Water vapor permeability testing demonstrated effective moisture resistance with the polymer coating. To evaluate the insulated cladding’s energy performance, we used the U.S. Department of Energy’s prototype single-family building model and simulated across 50 locations spanning 16 International Energy Conservation Code climate zones. The R-7 (R-value of 7 °F⋅ft 2 ⋅h/BTU per inch) retrofit cladding resulted in heating energy savings up to 275 therms (Fairbanks, AK) and cooling energy savings up to 1,547 kWh (Phoenix, AZ). The energy cost savings varied by region, but the highest annual cost savings ($\$$434/year) were observed in Santa Maria, CA, and the highest annual cost savings percentage (37 %) were noted in Monterey, CA. On a national scale, the insulated retrofit provided an average annual energy cost reduction of 16 %, highlighting the cladding system’s broad applicability and financial viability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Enhancement of conventional concrete mix designs for sensible thermal energy storage applications

The study examines twenty-nine different concrete mix designs with varying constituents to improve thermal performance for energy storage at elevated temperatures up to 420 °C. Effects of variables including the type and volumetric percentage of coarse and fine aggregates, the type and replacement content of supplemental cementitious materials, water-to-cement ratio, the type and quantity of steel fiber reinforcement, and the inclusion of iron oxide powder are experimentally investigated by measuring the mechanical and thermal properties of each mix, with the overall goal of enhancing thermal performance and mitigating mechanical degradation for thermal energy storage (TES) applications. It is found that the use of siliceous aggregate with a high volumetric percentage produces the highest improvement (23 %–37 % at elevated temperatures) of concrete thermal conductivity, while silica fume replacement of Type I cement provides the highest improvement (4 %–8 % at elevated temperatures) of concrete specific heat. To simulate the operation of a TES system, thermal cycling was conducted to examine the change in concrete properties as a function of repetitive heating (during and after 50 total cycles to 420 °C). Based on the results of testing, concrete mix designs with high aggregate percentages (up to 72 % by volume), siliceous coarse aggregate, silica fume replacement of Type I cement (15 % by weight), and steel fiber reinforcement (up to 2 % by volume) facilitate enhanced TES performance by providing consistent thermal conductivity of ~2.2 W/m·K and specific heat of ~3.2 MJ/m 3 ·K under cyclic high temperature exposure.

25 ENERGY STORAGE↗

Alkali-activated slag (AAS) and OPC-based composites containing crumb rubber aggregate: Physico-mechanical properties, durability and oxidation of rubber upon NaOH treatment

Value-added utilization of waste tires in cementitious materials has been studied for decades, whereas the synergy between rubber and alkali-activated cements deserves more investigations. To this end, we compared physico-mechanical and durability properties of alkali-activated slag (AAS) and OPC-based composites containing NaOH-pretreated/as-received crumb rubber (CR). It was found that the incorporation of CR had both positive and negative effects on specimens due to its special attributes. CR reduced electrical conductivity which was associated with the ion transport ability, since it worked as an electrical insulator and increased hydrophobicity of pore walls. The sulfate expansion decreased with CR content because the flow of sulfate ions was demobilized, and the flexibility of CR relieved the internal stress. CR also improved the freeze-thaw durability of composites if the total CR content was less than 30% in specimens. However, the low Young's modulus of CR impaired the compressive strength and failed to effectively control the total shrinkage upon drying. The composites with CR must avoid high temperature exposure which resulted in the pyrolysis of rubber. In addition, the NaOH pretreatment enhanced adhesion between CR and hydrated cement and improved overall performances of composites. The FTIR spectra confirmed the NaOH-induced accelerated oxidation of CR surface and the generation of polar functional groups including carbonyl and carboxyl groups, increasing the total surface energy of rubber. More importantly, the alkali-activation process for AAS could treat the CR aggregate in the meantime, which means the use of CR in alkali-activated cements does not require the pretreatment of CR before blending.

36 MATERIALS SCIENCE↗

Optimization of well design and CO 2 injection strategy for risk reduction in Class VI geological carbon sequestration wells

The safety and durability of Class VI wells are critical for geological carbon sequestration (GCS). However, current GCS operations face unique challenges: unlike traditional Class II wells, Class VI CO 2 injection wells operate at rates up to 100 times higher, dramatically increasing the risk of wellbore leakage and structural compromise due to severe temperature drops and associated mechanical stresses. Despite existing guidelines on material selection, there remains a substantial gap in understanding how rapid CO 2 injection rates, low surface temperatures, and variable reservoir conditions interact to threaten long-term well integrity. This study presents a comprehensive, original workflow integrating advanced analytical and numerical models for both well flow and well integrity analysis. By systematically simulating a wide range of field-relevant scenarios—including variations in injection rate, CO 2 temperature, and reservoir pressure—this work provides the first cross-validated assessment of cooling effects on wellbore. The results reveal that extreme temperature drops, up to 60 °C, can occur under high injection rates, particularly in depleted reservoirs, significantly increasing the risk of cement failure. Building on these insights, the study proposes innovative, practical well design and operational strategies, including ductile cement formulations, pre-stressing techniques, advanced insulation coatings, and proactive management of injection rates. The safety of Class VI well extends beyond simply using CO 2 resistant materials. Cement materials should possess optimal thermo-hydraulic-mechanical-chemical properties for effective performance. This work provides a scientific basis for optimizing Class VI well designs, with direct benefits for minimizing environmental risk, lowering operational costs, and enhancing the long-term reliability of GCS.

25 ENERGY STORAGE↗

Addressing wellbore integrity and thief zone permeability using microbially-induced calcium carbonate precipitation (MICP): A field demonstration

Microbially-induced calcium carbonate precipitation (MICP) is an emerging biotechnology for wellbore integrity applications including sealing defects in wellbore cement and modifying the permeability of rock formations. The goal of this field demonstration was to characterize a failed waterflood injection well and provide proof of principle that MICP can reduce permeability in the presence of oil using conventional oilfield fluid delivery methods. Here we compared well logs performed at the time the well was drilled with ultrasonic logs, sonic cement evaluation, and temperature logs conducted after the well failed. Analysis of these logs suggested that, rather than entering the target waterflood formation, injectate was traveling through defects in the well cement to a higher permeability sandstone layer above the target formation. Sporosarcina pasteurii cultures and urea-calcium media were delivered 2290 ft (698 m) below ground surface using a 3.75 gal (14.2 L) slickline dump bailer to promote mineralization in the undesired flow paths. By Day 6 and after 25 inoculum and 49 calcium media injections, the injectivity [gpm/psi] had decreased by approximately 70%. This demonstration shows that 1) common well logs can be used to identify scenarios where MICP can be employed to reduce system permeability, remediate leakage pathways, and improve waterflood efficiency, and 2) MICP can occur in the presence of hydrocarbons.

42 ENGINEERING↗

Building confidence in models for complex barrier systems for radionuclides

The modeling and simulation of the Cement-clay Interaction-Diffusion field (CI-D) experiment at the Mont Terri site in Switzerland presented here demonstrates that it is possible to capture the multiscale physical and chemical features of natural and engineered barrier systems for radionuclides. The simulations are successfully carried out with the newly developed CrunchODiTi high-performance computing software that accounts for multiple continua, including a continuum representing the electrical double layer (EDL) developed along negatively charged clay particles in clay rock. The simulation also accounts for both the complex three-dimensional (3D) geometry, expected as the norm in a geological waste repository, and the anisotropy of the geological formation. In addition, the high resolution of the model makes it possible to include "skin effects" developed at the interface between highly reactive materials, in this case between the high pH cement and the circumneutral but electrostatic Opalinus Clay. The successful history matching with the field experiment demonstrates that the distinct geochemical and physical properties of the cement and the Opalinus Clay in the CI-D experiment can be accounted for. Such analyses are essential for developing a defensible safety case for the underground storage of radioactive waste.

Sarsenbayev, Dauren↗

Sulphate resistance of low‐clinker engineered cementitious composites examined by MicroXRF imaging

Abstract Engineered cementitious composites (ECC) are a class of high‐performing fibre‐reinforced cementitious materials recognised for their increased ductility and durability compared to conventional cement‐based materials, owing to their autogenously controlled tight crack widths, even when subjected to high strains. To reduce ECC's environmental impact, this research examines the use of a low‐clinker binder − limestone‐calcined clay cement (LC3) − as an alternative to portland cement (PC), along with fly ash to further reduce the clinker proportion and the embodied CO 2 of the formulations. In conventional concrete, LC3 hydrates to a denser microstructure resulting from the synergistic reaction between limestone and calcined clay. At the lower water contents typical of ECC and with the presence of fly ash, the influence of the binder composition on the microstructure is difficult to anticipate. To examine the influence of these compositional variables on microstructure, permeability and durability, the sulphate resistance of LC3‐based ECC is explored. Specifically, the ECC‐LC3 blends are designed with high clinker replacement rate of 75% by mass of binder and contain either conventional fly ash or reclaimed fly ash at 50% by mass of binder. Expansion of ECC‐LC3 samples subjected to standard sodium sulphate test conditions was measured up to 12 months and the depth of penetration of sulphates into the ECC‐LC3 of varying compositions was quantified using micro‐X‐Ray Fluorescence (microXRF) imaging and modelling. The expansion results show that the ECC‐LC3 formulations performed better than the PC samples and can provide adequate resistance to external sulphate attack, even when reclaimed fly ashes are used in place of the conventional ash. In addition, the shallow penetration of sulphate into these cementitious composites demonstrates the low diffusion coefficients values that were determined using the quantitative data from MicroXRF imaging.

Microscopy↗

The nature and origins of decametre-scale porosity in Ordovician carbonate rocks, Halahatang oilfield, Tarim Basin, China

At >7 km depths in the Tarim Basin, hydrocarbon reservoirs in Ordovician rocks of the Yijianfang Formation contain large cavities ( c . 10 m or more), vugs, fractures and porous fault rocks. Although some Yijianfang Formation outcrops contain shallow (formed near surface) palaeokarst features, cores from the Halahatang oilfield lack penetrative palaeokarst evidence. Outcrop palaeokarst cavities and opening-mode fractures are mostly mineral filled but some show evidence of secondary dissolution and fault rocks are locally highly ( c . 30%) porous. Cores contain textural evidence of repeated formation of dissolution cavities and subsequent filling by cement. Calcite isotopic analyses indicate depths between c . 220 and 2000 m. Correlation of core and image logs shows abundant cement-filled vugs associated with decametre-scale fractured zones with open cavities that host hydrocarbons. A Sm–Nd isochron age of 400 ± 37 Ma for fracture-filling fluorite indicates that cavities in core formed and were partially cemented prior to the Carboniferous, predating Permian oil emplacement. Repeated creation and filling of vugs, timing constraints and the association of vugs with large cavities suggest dissolution related to fractures and faults. In the current high-strain-rate regime, corroborated by velocity gradient tensor analysis of global positioning system (GPS) data, rapid horizontal extension could promote connection of porous and/or solution-enlarged fault rock, fractures and cavities. Supplementary material: Stable isotopic analyses and the velocity gradient tensor and principal direction and magnitude calculation are available at https://doi.org/10.6084/m9.figshare.c.4946046 Thematic collection: This article is part of the The Geology of Fractured Reservoirs collection available at: https://www.lyellcollection.org/cc/the-geology-of-fractured-reservoirs

Geology↗

Global, Regional, and National Fossil-Fuel CO2 Emissions: 1751-2017

This data product is a time series of Carbon Dioxide (CO2) emissions from fossil fuel combustion and cement manufacture. Estimates of CO2 emissions are included for the globe and by nation back to 1751, and include emissions from solid fuel consumption, liquid fuel consumption, gas fuel consumption, cement production, and gas flaring. Per capita CO2 emissions and emissions from international trade (bunker fuels) are included as well; bunker fuels are not included in country totals, but are assigned to the country in which loading took place. Estimates are generated using the United Nations Energy Statistics database and the United States Geologic Survey’s cement statistics. Datasets produced from this group at Appalachian State University are located here, and are also located at https://energy.appstate.edu/research/work-areas/cdiac-appstate. Historic CDIAC data from Oak Ridge National Laboratory are located here: https://data.ess-dive.lbl.gov/view/doi:10.3334/CDIAC/00001_V2017. This dataset is the foundational dataset for the annual global carbon budget and other carbon cycle analyses that need relevant fossil fuel CO2 data. Within this data package are spreadsheets (.csv) of global and national estimates of CO2 emissions as well as text files of the ranking of each country’s total CO2 emissions and per capita for that year.

54 ENVIRONMENTAL SCIENCES↗

Saltstone third quarter calendar year 2019 (3QCY19) toxicity characteristic leaching procedure (TCLP) results

The aqueous waste from Tank 50 (salt solution) is sampled quarterly for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TAR-Z-00008, Revision 01, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the third quarter of calendar year 2019 (3QCY19). One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample”. Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Remediation (SRR). After a 28 day cure, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The 3QCY19 saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Engineered Barrier System R&D and International Collaborations – LANL (FY20): Spent Fuel and Waste Disposition

The United States Department of Energy’s Spent Fuel and Waste Disposition (SFWD) program is investigating the design and safety function of generic nuclear geologic repositories in a variety of geologic settings (salt, argillite, and crystalline rock). Different configurations and loadings of spent nuclear fuel and waste within disposal canisters are also being investigated, some of which have the potential to generate repository temperatures higher than previously considered (i.e., temperatures >100ºC) by foreign and domestic concepts. This report expands on engineered barrier material stability in a high temperature crystalline rock repository through high temperature hydrothermal experiments. Experiments were designed to develop engineered barrier system (EBS) concepts in a hightemperature crystalline environment in 1) bentonite-Grimsel Granodiorite interactions, 2) bentonite-cement reactions, and 3) interaction between waste canister materials and bentonite. Experiment results are applied to understanding long-term repository performance in terms of radionuclide isolation. One hydrothermal experiment was completed in the rocking autoclaves at LANL in FY-20: IEBS-6 (Grimsel Granodiorite + Wyoming bentonite + cured ordinary Portland cement + Grimsel Granodiorite synthetic groundwater, 250ºC/150 bar, 8 weeks). Several other experiments were planned but were delayed due to the COVID-19 pause in laboratory work. In addition, some characterization of the reaction products of experiments conducted in FY-20 was prevented by COVID-19. Mineral phase chemistry was not measured via electron microprobe analyses for IEBS-6. Quantitative X-ray diffraction results from IEBS-6 and HBT-1 were not completed. The missing analyses and discussion of the results will be included in next year’s report. New characterization that was completed includes scanning electron microscopy of reaction products from IEBS-6, quantitative X-ray diffraction results are presented from IEBS-1 through IBES-5, preliminary scanning electron microscope images and chemical analyses for IEBS-6, X-ray diffraction of the clay fraction from all experiments, measurement/imaging of mineral growth on the surface of steel coupons. Major observations pertaining to bentonite stability in a Grimsel Granodiorite environment include the stability of Na-montmorillonite at 250°C, the formation of trace CSH phases, and the formation of bentonite colloids on experiment cooling. The addition of a cured chip of Portland cement to the bentonite-Grimsel system results in slightly higher pH values and the formation of diverse secondary mineral phases that were not observed in the previous experiments (e.g., analcime, garronite, CSH phases). The new characterization efforts related to the interaction of stainless-steel coupons and bentonite clay focused on thickness and mineralogy of phases that formed at the steel surface. In Wyoming bentonite + Grimsel Granodiorite systems, newly formed minerals at the bentonitesteel coupon interface included alteration of the outermost steel edge to Fe,Cr-oxide phases, followed by Fe-rich phyllosilicates (Fe-saponite, chlorite) and interbedded Fe,Cr,Ni-sulfide phases (pentlandite). Hydrothermal experiments were completed to assess uranium-carbonate complexation at conditions relevant to high-temperature disposal. Autoclave solubility experiments were conducted at 150 to 250ºC with a range of carbonate and uranium concentrations. The experiment results were characterized via situ UV-Visible spectroscopy and synchrotron-based in situ XAS techniques. Results show a significant decrease in the stability of uranyl-carbonate complexes at temperatures above 100ºC along with the precipitation of uranium oxides. Further, at T > 200ºC, results show that uranyl-hydroxyl complexes control solubility of uranium instead of the previously predicted uranyl-carbonate species. These results are significant for understanding the mobility of uranium in the EBS, which will likely contain carbonate-rich fluids. International research efforts focused on three main areas: 1) participation in international conferences, 2) building collaborations with foreign repository programs, and 3) the initiation of an experimental program to complement the full-scale HotBENT test at the Grimsel test site. This experiment included Wyoming bentonite + low carbon steel + Grimsel Granodiorite synthetic groundwater and was run at the planned maximum temperature of the HotBENT test (200°C). Complete characterization of reaction products was hindered by disruptions to laboratory work but will be reported in the next FY. The experimental results obtained in FY-20 continue to document the wide-ranging effects of bulk composition and pressure-temperature conditions in the mineralogical and geochemical evolution of a high-temperature repository environment. Concepts developed will be used to inform models of long-term material stability in a generic crystalline rock-hosted repository.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Resiliency of Degraded Built Infrastructure

Infrastructure resiliency depends on the ability of infrastructure systems to withstand, adapt, and recover from chronic and extreme stresses. In this white paper, we address the resiliency of infrastructure assets and discuss improving infrastructure stability through development of our understanding of cement and concrete degradation. The resiliency of infrastructure during extreme events relies on the condition, adaptability, and recoverability of built infrastructure (roads, bridges, dams), which serves as the backbone of existing infrastructure systems. Much of the built infrastructure in the US has consistently been rated D+ by the American Society of Civil Engineers (ASCE). Aged infrastructure introduces risk to the system, since unreliable infrastructure increases the likelihood of failures under chronic and extreme stress and are particularly concerning when extreme events occur. To understand and account for this added risk from poor infrastructure quality, more research is needed on (i) how the changing environment alters the aging of new and existing built infrastructure and (ii) how degradation causes unique failure mechanisms. The aging of built infrastructure is based on degradation of the structural materials, such as concrete and steel supports, which causes failure. Current work in cement/concrete degradation is based on (i) the development of high strength and degradation resistance concrete mixtures, (ii) methods of assessing the age and reliability of existing structures, and (3) modeling of structural stability and the microstructural evolution of concrete/cement from degradation mechanisms (sulfide attack, carbonation, decalcification). Sandia National Laboratories (SNL) has made several investments in studying the durability and degradation of cement based materials, including using SNL-developed codes and methodologies (peridynamics, PFLOTRAN) to focus on chemo-mechanical fracture of cement for energy applications. Additionally, a recent collaboration with the University of Colorado Boulder has included fracture of concrete gravity dams, scaling the existing work to applications in full sized infrastructure problems. Ultimately, SNL has the experience in degradation of cementitious materials to extend the current research portfolio and answer concerns about the resilience of aging built infrastructure.

36 MATERIALS SCIENCE↗

A Scalable Process for Upcycling Carbon Dioxide (CO 2 ) and Coal Combustion Residues into Construction Products

Anthropogenic sources of carbon dioxide are generated from a number of sources, but the key among these are ordinary Portland cement (OPC) production and combustion of fossil fuels. Cement production is the largest global CO 2 source from the mineral decomposition of carbonates. Combination of the limestone decomposition and thermal requirements of the clinkering process causes cement production to contribute 8-9% of annual global CO 2 emissions. Combustion of fossil fuels (coal, oil and gas) was shown to contribute a much larger portion of global CO 2 emissions. As of 2018, combustion of fossil fuels accounted for 65% of global CO 2 , where 41% was derived from stationary sources for electricity and heat generation and the other 24% was related to transport. To reduce these contributions, key steps forward in CO 2 utilization technologies are required. The purpose of this project is to demonstrate the feasibility of the Reversa process evolving from a TRL-3 technology at the bench-scale up to TRL-6 technology at the pilot-scale. The reliability of the Reversa technology was tested to prove the effective production of concrete masonry units (CMUs) at bench scale, where the units exceeded the required 13.8 MPa compressive strength requirements. The overall goal of this project was to accelerate the development of a CO 2 mineralization process that synergistically utilizes CO 2 in flue gas and coal combustion residues (CCRs) to synthesize carbonated concrete, a functional replacement for traditional concrete. The culmination of this work resulted in 12 successful production runs at the Integrated Test Center (ITC), Gillette, WY using coal flue gas as a CO 2 source. This was followed by 6 production runs which were completed at the National Carbon Capture Center (NCCC), Wilsonville, AL, using coal-fired and natural gas (NG) flue gas as the CO 2 source. Over the course of the production runs at NCCC and ITC, the CO 2 utilization as a function of time, 24-h CO 2 uptake, electricity usage, and 28-d net area compressive strength recorded for each run. The ITC and NCCC demonstrations achieved an average of 0.19 and 0.1 g CO 2 /g reactant, respectively. Both demonstrations exceeded the project’s target goals of uptake > 0.05 g CO 2 /g reactant. Average compressive strength of the ITC blocks was 18.24 MPa at 28-days. This exceeded the target strength of 13.8 MPa specified by ASTM C90. ITC and NCCC produced an average CO 2 utilization efficiency of 74.9 and 57.9%, respectively. Both demonstration averages were within the target range of 50 to 90% utilization efficiency. For some production runs the NCCC demo did exceeded the a CO 2 utilization efficiency of 75%. An LCA of the Reversa process compared to an industry standard product revealed a net CO 2 reduction of 39% to 42%. This exceeded the target requirement of >25% net CO 2 reduction. Collection of this data was used to determine that the project was successful as the demonstration goals were achieved: (1) achieving in excess of 75% CO 2 utilization efficiency, (2) utilizing greater than 250 kg of CO 2 per production batch/run, and (3) ensuring compliance of carbonated blocks with industry standard specifications (ASTM C90).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Saltstone First Quarter Calendar Year 2021 (1QCY21) Toxicity Characteristic Leaching Procedure (TCLP) Results

The aqueous waste from Tank 50 (salt solution) is sampled quarterly for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TTR-Z00023, Revision 0, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the first quarter of calendar year 2021(1QCY21). One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample”. Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Remediation (SRR). After at least 28 days cured, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The 1QCY21 saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC that was in effect at the time of the tank sampling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Saltstone Third Quarter Calendar Year 2021 (3QCY21) Toxicity Characteristic Leading Procedure (TCLP) Results

The aqueous waste from Tank 50 (salt solution) is sampled quarterly for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TTR-Z-00023, Revision 0, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the third quarter of calendar year 2021(3QCY21). One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample”. Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Remediation (SRR). After at least 28 days cured, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The 3QCY21 saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC that was in effect at the time of the tank sampling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

January 2022 Semiannual Saltstone Toxicity Characteristic Leaching Procedure (TCLP) Results

The aqueous waste from Tank 50 (salt solution) is sampled semiannually for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TTR-Z-00025, Revision 0, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the January 2022 semiannual Toxicity Characteristic Leaching Procedure (TCLP) samples. One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample.” Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Mission Completion (SRMC). After at least 28 days cured, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The January 2022 semiannual saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC that was in effect at the time of the tank sampling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗