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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.

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At least 1,171 records · Page 65
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Emerging Strategies for Modifying Lignin Chemistry to Enhance Biological Lignin Valorization

Biological lignin valorization represents a promising approach contributing to sustainable and economic biorefineries. Here, the low level of valuable lignin–derived products remains a major challenge hindering the implementation of microbial lignin conversion. Lignin's properties play a significant role in determining the efficiency of lignin bioconversion. To date, despite significant progress in the development of biomass pretreatment, lignin fractionation, and fermentation over the last few decades, little efforts have gone into identifying the ideal lignin substrates for an efficient microbial metabolism. In this Minireview, emerging and state–of–the–art strategies for biomass pretreatment and lignin fractionation are summarized to elaborate their roles in modifying lignin structure for bioconversion. Fermentation strategies aimed at enhancing lignin depolymerization for microbial utilization are systematically reviewed as well. With an improved understanding of the ideal lignin structure elucidated by comprehensive metabolic pathways and/or big data analysis, modifying lignin chemistry could be more directional and effective. Ultimately, together with the progress of fermentation process optimization, biological lignin valorization will become more competitive in biorefineries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Sustainable Direct Recycling of Lithium-Ion Batteries via Solvent Recovery of Electrode Materials

Separation of electrode materials from their current collectors is an enabling step toward recovering critical materials from spent lithium-ion batteries. In this study, a highly efficient, cost-effective, and environmentally sustainable separation process was developed for that purpose. Ethylene glycol, a vital commodity chemical as an antifreeze and polymer precursor, is used to delaminate electrode materials at low temperatures in seconds without altering the crystalline structure and morphology of active electrode materials. The recovered current collectors were intact without any corrosion. The authors also found that the solvent could be continuously reused, leading to the development of a closed-loop ecosystem and lithium-ion battery circular economy. The ultrafast delamination was driven by the competitive inhibition of binding through the weakening of hydrogen bonding. The ethylene glycol-based separation is a sustainable electrode recovery process that paves the way for battery recycling.

25 ENERGY STORAGE↗
DOE OSTI2021

Reducing Antisolvent Use in the STRAP Process by Enabling a Temperature–Controlled Polymer Dissolution and Precipitation for the Recycling of Multilayer Plastic Films

The recently reported processing strategy called solvent-targeted recovery and precipitation (STRAP) enables deconstruction of multilayer plastic packaging films into their constituent resins by selective dissolution. It uses a series of solvent washes that are guided by thermodynamic calculations of polymer solubility. In this work, the use of antisolvents in the STRAP process was reduced and solvent mixtures were considered to enable the temperature-controlled dissolution and precipitation of the target polymers in multilayer films. This was considered as a means to further improve the STRAP process and its estimated costs. Two STRAP approaches were compared based on different polymer precipitation techniques: precipitation by the addition of an antisolvent (STRAP-A) and precipitation by decreasing the solvent temperature (STRAP-B). Both approaches were able to separate the constituent polymers in a post-industrial film composed primarily of polyethylene (PE), ethylene vinyl alcohol (EVOH), and polyethylene terephthalate (PET) with near 100 % material efficiency. Technoeconomic analysis indicates that the minimum selling price (MSP) of the recycled resins with STRAP-B is 21.0 % lower than that achieved with STRAP-A. This provides evidence that thermally driven polymer precipitation is an option to reduce the use of antisolvents, making the STRAP process more economically and environmentally attractive. A third process, STRAP-C, was demonstrated with another post-industrial multilayer film of a different composition. Here, the results demonstrate that this process can also recover polymers at similar costs to those of virgin resins, indicating that the STRAP technology is flexible and can remain economically competitive as the plastic feed complexity is increased.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Hydrazine Energy Storage: Displacing N 2 H 4 from the Metal Coordination Sphere

Hydrogen carriers, such as hydrazine (N 2 H 4 ), may facilitate long duration energy storage, a vital component for resilient grids by enabling more renewable energy generation. Lanthanide coordination chemistry with N 2 H 4 as well as efforts to displace N 2 H 4 from the metal coordination sphere to develop an efficient catalytic production cycle were detailed. Modeling the equilibrium of different ligand coordination, it was predicted that strong sigma donor molecules would be required to displace N 2 H 4 . Monitoring competition experiments with nuclear magnetic resonance confirmed that trimethyl phosphine oxide, dimethylformamide, and dimethyl sulfoxide displaced N 2 H 4 in large or small lanthanide complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Optimizing Renewable Ammonia Production for a Sustainable Fertilizer Supply Chain Transition

Local renewable ammonia production using electrolytic hydrogen is an emerging approach to alleviate emissions attributed to synthetic nitrogen fertilizer production while also insulating against fluctuations in fertilizer prices and mitigating transportation costs and emissions. However, replacing ammonia currently produced using fossil fuels will not be immediate. To this end, we develop a supply chain transition model, which first optimizes the design and hourly operation of new renewable ammonia facilities to minimize production costs and then optimizes the annual installation timing, production scale, and location of these new renewable facilities along with ammonia transportation to meet county resolution demands. The objective is to augment and eventually replace conventional ammonia market imports in an economically competitive manner. We performed a case study for Minnesota's ammonia supply chain and found that a full transition to in-state renewable production by 2032 is optimal. This is incentivized by the U.S. federal government's clean hydrogen production credits. This transition results in 99 % reduction in carbon intensity along with stable supply costs below $475 per metric tonne. New renewable production facilities are an order of magnitude smaller than existing conventional plants. They use both wind and solar resources and operate dynamically to minimize expensive battery and hydrogen storage capacities.

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

The Significance of the 'Insignificant': Non-covalent Interactions in CO 2 Reduction Reactions with 3C-TM (TM=Sc-Zn) Single-Atom Catalysts

With energy shortages and excessive CO 2 emissions driving climate change, converting CO 2 into high-value-added products offers a promising solution for carbon recycling. We investigate CO 2 reduction reactions (CO2RR) catalyzed by 10 single-atom catalysts (SACs), incorporating weak non-covalent interactions, specifically lone pair-π and H-π interactions. The SACs, consisting of transition metals coordinated by three carbon atoms in a defective graphene substrate (3C-TM, TM=Sc-Zn), leverage these interactions to influence the energy fluctuations of intermediates and the limiting potentials of CO 2 RR, without altering the overall reaction pathway. Further, our findings show that SACs based on early transition metals (Sc, Ti, V, Cr) can serve as catalysts for C 1 products, including HCOOH, HCHO, CH 3 OH, and CH 4 , while those based on Fe and Co are suitable for CO formation. Driving force analysis helps bridge theoretical results with experimental observations and propose a modified approach for assessing hydrogen evolution reactions (HER) competition. SACs based on Ni and Cu exhibit moderate HER tolerance, while early transition metals excel in selective CO 2 reduction. We also identify a linear scaling relationship between the free energies of *COOH and *CO. This study offers valuable insights for future experimental studies and large-scale computational screenings.

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

Closed‐Loop Recyclable Vitrimer Plastics from PET Waste: A Design for Circularity

Plastics are essential to modern society, but their low recycling rates and inefficient end-of-life management pose a significant environmental challenge. Herein, the efficient strategy for upcycling postconsumer poly(ethylene terephthalate) (PET) waste into robust, closed-loop recyclable vitrimer plastics and composites is presented to address this issue. The catalyst-free aminolysis utilizes readily available amines to deconstruct diverse PET wastes into macromonomers, which are upcycled into vitrimers, exhibiting superior mechanical properties and exceeding the ultimate tensile stress and Young's Modulus of virgin PET by 80% and 150% respectively. These vitrimers exhibit excellent healability, shape memory, thermal reprocessability, and closed-loop chemical recyclability, enabling quantitative macromonomer recovery even from mixed plastic waste streams and glass/carbon fiber reinforced vitrimer (G/CFRV) composites. Furthermore, the vitrimer resin yields robust GFRV and CFRV composites with tensile strengths exceeding those of traditional epoxy composites by 100% and 80%, respectively, while maintaining complete chemical recyclability of both constituent materials. A preliminary technoeconomic analysis confirms the costeffectiveness and competitiveness of the facile PET deconstruction approach, which is potentially adaptable to other condensation polymers. Further, this study presents a facile approach to upcycling plastic waste into circular plastics and composites, offering a sustainable solution to global plastic waste management and fostering a circular economy.

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

Allometric relationships and trade‐offs in 11 common M editerranean‐climate grasses

Abstract Biomass allocation in plants is the foundation for understanding dynamics in ecosystem carbon balance, species competition, and plant–environment interactions. However, existing work on plant allometry has mainly focused on trees, with fewer studies having developed allometric equations for grasses. Grasses with different life histories can vary in their carbon investment by prioritizing the growth of specific organs to survive, outcompete co‐occurring plants, and ensure population persistence. Further, because grasses are important fuels for wildfire, the lack of grass allocation data adds uncertainty to process‐based models that relate plant physiology to wildfire dynamics. To fill this gap, we conducted a greenhouse experiment with 11 common California grasses varying in photosynthetic pathway and growth form. We measured plant sizes and harvested above‐ and belowground biomass throughout the life cycle of annual species, while for the establishment stage of perennial grasses to quantify allometric relationships for leaf, stem, and root biomass, as well as plant height and canopy area. We used basal diameter as a reference measure of plant size. Overall, basal diameter is the best predictor for leaf and stem biomass, height, and canopy area. Including height as another predictor can improve model accuracy in predicting leaf and stem biomass and canopy area. Fine root biomass is a function of leaf biomass alone. Species vary in their allometric relationships, with most variation occurring for plant height, canopy area, and stem biomass. We further explored potential trade‐offs in biomass allocation across species between leaf and fine root, leaf and stem, and allocation to reproduction. Consistent with our expectation, we found that fast‐growing plants allocated a greater fraction to reproduction. Additionally, plant height and specific leaf area negatively influenced the leaf‐to‐stem ratio. However, contrary to our hypothesis, there were no differences in root‐to‐leaf ratio between perennial and annual or C 4 and C 3 plants. Our study provides species‐specific and functional‐type‐specific allometry equations for both above‐ and belowground organs of 11 common California grass species, enabling nondestructive biomass assessment in California grasslands. These allometric relationships and trade‐offs in carbon allocation across species can improve ecosystem model predictions of grassland species interactions and environmental responses through differences in morphology.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Carbon cycling across ecosystem succession in a north temperate forest: Controls and management implications

Despite decades of progress, much remains unknown about successional trajectories of carbon (C) cycling in north temperate forests. Drivers and mechanisms of these changes, including the role of different types of disturbances, are particularly elusive. To address this gap, we synthesized decades of data from experimental chronosequences and long-term monitoring at a well-studied, regionally representative field site in northern Michigan, USA. Our study provides a comprehensive assessment of changes in above- and belowground ecosystem components over two centuries of succession, links temporal dynamics in C pools and fluxes with underlying drivers, and offers several conceptual insights to the field of forest ecology. Our first advance shows how temporal dynamics in some ecosystem components are consistent across severe disturbances that reset succession and partial disturbances that slightly modify it: both of these disturbance types increase soil N availability, alter fungal community composition, and alter growth and competitive interactions between short-lived pioneer and longer-lived tree taxa. Further, these changes in turn affect soil C stocks, respiratory emissions, and other belowground processes. Second, we show that some other ecosystem components have effects on C cycling that are not consistent over the course of succession. For example, canopy structure does not influence C uptake early in succession but becomes important as stands develop, and the importance of individual structural properties changes over the course of two centuries of stand development. Third, we show that in recent decades, climate change is masking or overriding the influence of community composition on C uptake, while respiratory emissions are sensitive to both climatic and compositional change. In synthesis, we emphasize that time is not a driver of C cycling; it is a dimension within which ecosystem drivers such as canopy structure, tree and microbial community composition change. Changes in those drivers, not in forest age, are what control forest C trajectories, and those changes can happen quickly or slowly, through natural processes or deliberate intervention. Stemming from this view and a whole-ecosystem perspective on forest succession, we offer management applications from this work and assess its broader relevance to understanding long-term change in other north temperate forest ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Spatial Bayesian models project shifts in suitable habitat for Pacific Northwest tree species under climate change

Abstract We developed spatial Bayesian hierarchical models to assess potential climate change impacts on suitable habitat for five important tree species in the Pacific northwestern United States (California, Oregon, and Washington). Individual‐species models were fit with presence–absence data from forest inventory field plots and spatial relationships were specified through a conditional autoregressive model. This modeling approach allowed us to visualize uncertainty in response curves, map current and future prediction uncertainty, and provide interval estimates for change. Upward elevational or northward latitudinal shifts in climatically suitable habitat were projected for all species. Climate change impacts were the most damaging for noble fir ( Abies procera ), for which 79%–100% of the current range was projected to become climatically unsuitable by the 2080s. Although coastal Douglas‐fir ( Pseudotsuga menziesii var. menziesii ) has been projected by others to gain habitat in Canada, within our study area we projected a net loss of climatically suitable habitat (ca. 8000–31,400 km 2 ) under three of four future climate scenarios. A net loss in habitat was also projected for Oregon white oak ( Quercus garryana ) under three of four scenarios, with 40%–60% of the current range becoming unsuitable. Although there was no net loss of habitat for forest land blue oak under any scenario, other factors like competition may inhibit blue oak ( Quercus douglasii ) and white oak from occupying areas projected to increase in climatic suitability. Additionally, between 13% and 32% of blue oak's current range was projected to become unsuitable; some of these areas aligned with dieback following the 2012–2015 California drought, which our data set predates. Unlike the other four species, we projected a 17%–25% increase in climatically suitable habitat for California black oak ( Quercus kelloggii ), although 1%–20% of the current range was still projected to become unsuitable. Our findings indicate that, although some species will face more pressure in tracking climatically suitable habitat than others, climate change will impact the location of suitable habitat for many species.

Kralicek, Karin↗
DOE OSTI2025

Functional but not taxonomic diversity increases productivity of Populus in the southeastern United States

Plant interactions like competition and facilitation impact ecosystem function and resilience. Improving our understanding of the relationships between these interactions and community productivity has important implications for managers of production systems in forestry and agriculture as well as conservation science. Populus spp. are an excellent model system for exploring how inter‐ and intraspecific interactions impact ecosystem functions, such as productivity, in forest plantations. In this study, we compared aboveground productivity of six Populus clones from three different taxa grown in monoclonal and mixed‐clonal plots. The different mixture treatments were intended to experimentally test aboveground biomass response to contrasting levels of taxonomic diversity and functional diversity based on nitrogen use characteristics of Populus clones. We hypothesize that functional diversity would be more important than taxonomic diversity in increasing aboveground productivity of mixed‐clonal plantings compared to monocultures. In addition, a subset of treatments was carried out on additional sites representing a productivity gradient in order to determine if the relationship between biodiversity and productivity in these systems diminished at more productive sites as suggested by the stress‐gradient hypothesis. We found that functionally diverse mixtures of clones had greater yield of aboveground biomass than the average of their constituent monocultures, while more taxonomically diverse mixes of clones did not differ from the average of their constituent monocultures. However, when reestablished on sites with extremely high or low productivity, the best performing clone mixture also did not differ from the average of its constituent monocultures. Our results suggest that intimate clone mixtures of Populus have the potential to significantly increase productivity, but results vary by mixture and by site. To capitalize on positive biodiversity effects on yield in production systems, targeted mixtures based on divergent functional traits linked to different use and acquisition strategies for site‐specific limiting resources are most likely to be successful.

BEF↗
DOE OSTI2021

Functional traits driving species role in the structure of terrestrial vertebrate scavenger networks

Abstract Species assemblages often have a non‐random nested organization, which in vertebrate scavenger (carrion‐consuming) assemblages is thought to be driven by facilitation in competitive environments. However, not all scavenger species play the same role in maintaining assemblage structure, as some species are obligate scavengers (i.e., vultures) and others are facultative, scavenging opportunistically. We used a database with 177 vertebrate scavenger species from 53 assemblages in 22 countries across five continents to identify which functional traits of scavenger species are key to maintaining the scavenging network structure. We used network analyses to relate ten traits hypothesized to affect assemblage structure with the “role” of each species in the scavenging assemblage in which it appeared. We characterized the role of a species in terms of both the proportion of monitored carcasses on which that species scavenged, or scavenging breadth (i.e., the species “normalized degree”), and the role of that species in the nested structure of the assemblage (i.e., the species “paired nested degree”), therefore identifying possible facilitative interactions among species. We found that species with high olfactory acuity, social foragers, and obligate scavengers had the widest scavenging breadth. We also found that social foragers had a large paired nested degree in scavenger assemblages, probably because their presence is easier to detect by other species to signal carcass occurrence. Our study highlights differences in the functional roles of scavenger species and can be used to identify key species for targeted conservation to maintain the ecological function of scavenger assemblages.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Tuning Structural and Electronic Configuration of FeN 4 via External S for Enhanced Oxygen Reduction Reaction

The Fe–N–C material represents an attractive oxygen reduction reaction electrocatalyst, and the FeN 4 moiety has been identified as a very competitive catalytic active site. Fine tuning of the coordination structure of FeN 4 has an essential impact on the catalytic performance. Herein, we construct a sulfur‐modified Fe–N–C catalyst with controllable local coordination environment, where the Fe is coordinated with four in‐plane N and an axial external S. The external S atom affects not only the electron distribution but also the spin state of Fe in the FeN 4 active site. The appearance of higher valence states and spin states for Fe demonstrates the increase in unpaired electrons. With the above characteristics, the adsorption and desorption of the reactants at FeN 4 active sites are optimized, thus promoting the oxygen reduction reaction activity. This work explores the key point in electronic configuration and coordination environment tuning of FeN 4 through S doping and provides new insight into the construction of M–N–C‐based oxygen reduction reaction catalysts.

25 ENERGY STORAGE↗
DOE OSTI2020

Evolution of Electric Sector Water Use Under Alternative Electricity Futures

Increasing competition for water resources in the United States could create future challenges for allocating and using thermal cooling water in the U.S. electric power sector. While thermal power plant retirements and the growth of wind and solar technologies can reduce national aggregate power sector cooling water use, local water constraints and growing demand for agricultural or municipal supply could create greater needs for higher-cost alternative water supplies such as groundwater or recycled wastewater. For some regions, these incentives could change future electricity planning and operational decisions. These relationships and impacts are studied here using the National Renewable Energy Laboratory (NREL) Regional Energy Deployment System (ReEDS), a national electric sector planning model that has recently been upgraded to include a highly detailed representation of thermal cooling water demand and supply. Thermal power technologies are differentiated by both cooling technology and water source type to track and constrain thermal cooling water use in a way that incorporates both physical and legal water considerations in the United States. This capability is exercised under a range of electricity sector futures with alternative technology costs, fuel prices, and water constraints to illustrate ways that U.S. electric sector water use could evolve under uncertain future electric sector drivers. In exploring changes to regional generation and transmission planning and operation, water requirements, and cost, we highlight the environmental and economic impacts of future power sector water decisions.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2020

Toward Validation of Toxicological Interpretation of Diffusive Gradients in Thin Films in Marine Waters Impacted by Copper

Determination of Mytilus galloprovincialis larvae median effect concentration (EC50), of Cu in coastal marine waters by diffusive gradient in thin-films (DGT), has been shown to effectively reduce the need to consider dissolved organic carbon (DOC) concentration and quality. West coast marine and estuarine organisms’ chronic toxicity test protocol was used to validate previously modelled protective effects, afforded to highly sensitive marine larvae by ligand competition, in five diverse site waters. The results demonstrate significant narrowing of toxicological endpoints, where EC50s ranged from 3.74 – 6.67 µg/L as CDGT Cu versus 8.76 – 26.8 µg/L as CuDISS over a DOC range of 0.74 – 3.11 mg/L. Additionally, DOC quality (characterized by fluorescence excitation and emission matrices) indicates that the heterogeneity of competing Cu binding ligands, in common marine waters, minimizes the need for class determinations toward explaining the degree of protection, when assumptions in criterion maximum concentration (CMC) setting are conservative. A CDGT Cu EC50 of 3.7 µg/L, and corresponding CMC CDGT Cu of 1.8 µg/L, for universal application by regulatory compliance-monitoring programs, are proposed as a superior approach toward both integration of dynamic water quality over effective exposure periods and quantification of biologically-relevant trace Cu speciation and are demonstrated by in situ data.

Diffusive Gradients in Thin-films, copper, seawate↗
DOE OSTI2021

Carbon capture, utilization, and storage hub development on the Gulf Coast

Abstract The Gulf Coast of the United States hosts diverse power generation, refining, and petrochemical processing facilities, resulting in the nation's largest volumetric concentration of industrial CO 2 emissions, rivaled only by the Ohio River Valley. These emissions sources are concentrated in specific industrial clusters that allow combining emissions streams to achieve economies of scale. The region is currently undergoing globally significant industrial expansion and investment as a result of abundant and inexpensive regional unconventional natural gas availability, and is a growing exporter of liquefied natural gas (LNG). Opportunities to integrate CO 2 emission management within the diverse energy chains in the region are volumetrically significant and include both concentrated and dilute sources. Significant examples of capture, transport, and storage exist. Offshore storage is particularly attractive, as it provides simplified land leasing models (single governmental land owner), proven reservoir quality, and presents fewer risks to both protected groundwater and populated areas. Projects can now take advantage of recently expanded opportunities under section 45Q of the Internal Revenue Service tax code. The region continues to evolve as an active carbon‐handling hub, and is uniquely suited to justify additional investment in carbon capture, utilization, and storage (CCUS) technologies via a large‐scale integrated project development. Continued development of integrated projects will allow the region to continue to grow economically within its strong fossil‐fuel handling competence focus while advancing low‐carbon energy technologies that maintain globally competitiveness. © 2021 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.

45Q↗
DOE OSTI2021

Establishment of time‐resolved fluoroimmunoassay of IgG4 based on magnetic microspheres

Abstract Background The abnormal increase in serum IgG4 level is an important clinical symptom of IgG4‐related disease (IgG4‐RD), and the detection of serum IgG4 level is a powerful tool for the diagnosis of IgG4‐RD. This study was conducted to establish a simple and rapid immunoassay for the determination of human serum IgG4 levels. Methods Based on the competition method, a novel immunoassay was established for the determination of human serum IgG4 using a combination of time‐resolved fluoroimmunoassay (TRFIA) and magnetic microspheres. IgG4 was coupled with magnetic microspheres and competed with IgG4 in the samples to bind the Eu 3+ ‐labeled anti‐IgG4 antibody. The immunocomplex was separated and washed in a magnetic field, and the fluorescence counts were measured according to the number of dissociated europium ions. Results The analytical sensitivity of IgG4‐TRFIA based on magnetic microspheres was 0.006 g/L, and the detection range was 0.006–20 g/L under optimal conditions. The precision, recovery, and specificity of this immunoassay were demonstrated to be acceptable. The clinical application of IgG4‐TRFIA based on magnetic microspheres was evaluated and compared with that of immunonephelometry. The results showed that the two detection methods had a good correlation, with a correlation coefficient of .9871. Conclusion IgG4‐TRFIA based on magnetic microspheres has the advantages of high sensitivity, wide detection range, and short analysis time and has the potential to become a useful tool for the diagnosis of IgG4‐RD.

Wu, Qingqing↗
DOE OSTI2020

Identifying the mechanisms of cation inhibition of phenol oxidation by acid birnessite

Abstract Many phenolic compounds found as contaminants in natural waters are susceptible to oxidation by manganese oxides. However, there is often variability between oxidation rates reported in pristine matrices and studies using more environmentally relevant conditions. For example, the presence of cations generally results in slower phenolic oxidation rates. However, the underlying mechanism of cation interference is not well understood. In this study, cation co‐solutes inhibit the transformation of four target phenols (bisphenol A, estrone, p ‐cresol, and triclosan) by acid birnessite. Oxidation rates for these compounds by acid birnessite follow the same trend (Na + > K + > Mg 2+ > Ca 2+ ) when cations are present as co‐solutes. We further demonstrate that the same trend applies to these cations when they are absent from solution but pre‐exchanged with the mineral. We analyze valence state, surface area, crystallinity, and zeta potential to characterize changes in oxide structure. The findings of this study show that pre‐exchanged cations have a large effect on birnessite reactivity even in the absence of cation co‐solutes, indicating that the inhibition of phenolic compound oxidation is not due to competition for surface sites, as previously suggested. Instead, the reaction inhibition is attributed to changes in aggregation and the mineral microstructure.

Balgooyen, Sarah↗