Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “nitrate”

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

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

At least 667 records · Page 37
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Molecular and Dual-Isotopic Profiling of the Microbial Controls on Nitrogen Leaching in Agricultural Soils under Managed Aquifer Recharge

Nitrate (NO 3 – ) leaching is a serious health and ecological concern in global agroecosystems, particularly those under the application of agricultural-managed aquifer recharge (Ag-MAR); however, there is an absence of information on microbial controls affecting NO 3 – leaching outcomes. We combine natural dual isotopes of NO 3 – ( 15 N/ 14 N and 18 O/ 16 O) with metagenomics, quantitative polymerase chain reaction (PCR), and a threshold indicator taxa analysis (TITAN) to investigate the activities, taxon profiles, and environmental controls of soil microbiome associated with NO 3 – leaching at different depths from Californian vineyards under Ag-MAR application. The isotopic signatures demonstrated a significant priming effect (P < 0.01) of Ag-MAR on denitrification activities in the topsoil (0–10 cm), with a 12–25-fold increase of 15 N–NO 3 – and 18 O–NO 3 – after the first 24 h of flooding, followed by a sharp decrease in the enrichment of both isotopes with ~80% decline in denitrification activities thereafter. In contrast, deeper soils (60–100 cm) showed minimal or no denitrification activities over the course of Ag-MAR application, thus resulting in 10–20-fold of residual NO 3 – being leached. Metagenomic profiling and laboratory microcosm demonstrated that both nitrifying and denitrifying groups, responsible for controlling NO 3 – leaching, decreased in abundance and potential activity rates with soil depth. TITAN suggested that Nitrosocosmicus and Bradyrhizobium, as the major nitrifier and denitrifier, had the highest and lowest tipping points with regard to the NO 3 – changes (P < 0.05), respectively. Overall, our study provides new insight into specific depth limitations of microbial controls on soil NO 3 – leaching in agroecosystems.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Life Cycle Emissions and Health Cost Impacts of Producing Ethanol and Electricity from Willow and Switchgrass in the Riparian Buffers of Mid-Atlantic United States

The United States (US Mid-Atlantic Region (MAR) has the potential to grow a variety of perennial feedstocks such as switchgrass and shrub willow to increase domestic energy production. These cellulosic feedstocks have also shown improved ecosystem services, such as soil carbon sequestration, nitrate leaching reduction, and flood mitigation along rivers and streams as partially harvested riparian buffers. To examine the effects on greenhouse gases (GHGs) and criteria air pollutants (CAPs) from using these feedstocks to produce ethanol or electricity, we conducted a comprehensive life cycle assessment (LCA) and estimated the impact on human health costs when land use is changed from corn production for ethanol. Results indicate up to 54% reduced GHG per hectare from using willow and switchgrass feedstock sources to produce ethanol instead of corn. However, there was a trade-off in terms of CAP emission, as grass-based energy emitted more NO x and SO x compared to the corn ethanol pathway, except for SO X emissions from willow-based electricity. Electricity from cellulosic biomass had higher particulate matter (PM) emission compared to that from corn ethanol. Estimates for health cost to society ranged from $2498 ha –1 for electricity from switchgrass to a net benefit of $448 ha –1 for ethanol production from willow, depending on varying biomass yield under different market scenarios. Although using cellulosic feedstocks to produce bioenergy has great potential to reduce GHG emissions, CAP control measures are needed to manage CAP-induced health costs.

Bioenergy↗
DOE OSTI2025

How do Hydrological Variability and Human Activities Control the Spatiotemporal Changes of Riverine Nitrogen Export in the Upper Mississippi River Basin?

Excessive nitrogen export from agricultural watersheds remains a critical water quality challenge, with the Upper Mississippi River Basin (UMRB) significantly contributing to downstream eutrophication and hypoxia in the Gulf. This study investigates the spatiotemporal dynamics of riverine nitrate plus nitrite (NO 3 − + NO 2 − -N) export across the UMRB at high spatial resolution (12-digit Hydrologic Unit Codes or HUC12 subwatershed scale) during 2001−2020 and quantifies the effects of anthropogenic activities and hydrological variability on riverine NO 3 − + NO 2 − -N export changes in the region between 2001−2005 and 2016−2020. Our results revealed hotspots of substantial increases in NO 3 − + NO 2 − -N yields across the UMRB, with distinct regional patterns in driving factors. Over the entire UMRB, NO 3 − + NO 2 − -N yields increased by 9.7 kg/ha/yr on average from 2001−2005 to 2016−2020, with anthropogenic activities contributing 4.8 kg/ha/yr and hydrological variability contributing 4.9 kg/ha/yr. The northern and western UMRB had combined influences from both anthropogenic activities and hydrological variability, while the east-central regions had predominantly hydrologically driven changes. Agricultural sources, including fertilizer, manure, and biological nitrogen fixation, collectively contributed over 80% of NO 3 − + NO 2 − -N loading throughout the basin. Furthermore, this framework for disentangling human and hydrological impacts provides critical insights for developing effective and targeted watershed management strategies to reduce nutrient losses and improve water quality.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

UV–Vis–NIR Reflectance Spectroscopy and Chemometrics for Monitoring Pu Directly on an Ion Exchange Column

Here, we present a fiber-optic UV–vis–NIR reflectance spectroscopy method for direct, noninvasive monitoring of Pu(IV) in a glass ion exchange column during dynamic loading and elution in a glovebox. A movable probe enables spatially resolved spectral acquisition along the column axis, capturing distinct features associated with Pu(IV) nitrate complexes during loading and free ions during elution. Principal component analysis was applied to extract the dominant spectral variance and resolve relative concentration profiles without requiring precise knowledge of optical penetration depth or species identity. This in situ approach reveals spatial gradients and speciation dynamics in real time, which provides actionable insight into Pu(IV) ion migration, resin saturation, and breakthrough behavior under evolving flow conditions. The method offers a practical, fiber-compatible strategy to monitor glass column–based separations for Pu and other lanthanides or actinides and to characterize metal–resin interactions in flow-through systems.

actinide↗
DOE OSTI2021

La 2 Zr 2 O 7 Nanoparticle-Mediated Synthesis of Porous Al-Doped Li 7 La 3 Zr 2 O 12 Garnet

In this work, we modified the reaction pathway to quickly (minutes) incorporate lithium and stabilize the ionic conducting garnet phase by decoupling the formation of a La–Zr–O network from the addition of lithium. To do this, we synthesized La 2 Zr 2 O 7 (LZO) nanoparticles to which LiNO 3 was added. This method is a departure from typical solid-state synthesis methods that require high-energy milling to promote mixing and intimate particle–particle contact and from sol–gel syntheses as a unique porous microstructure is obtained. We show that the reaction time is limited by the rate of nitrate decomposition and that this method produces a porous high-Li-ion-conducting cubic phase, within an hour, that may be used as a starting structure for a composite electrolyte.

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

Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

Despite the significant impact of radiation-induced redox reactions on the accessibility and lifetimes of actinide oxidation states, fundamental knowledge of aqueous actinide metal ion radiation chemistry is limited, especially for the late actinides. A quantitative understanding of these intrinsic radiation-induced processes is essential for investigating the fundamental properties of these actinides. We present here a picosecond electron pulse reaction kinetics study into the radiation-induced redox chemistry of trivalent berkelium (Bk(III)) and californium (Cf(III)) ions in acidic aqueous solutions at ambient temperature. New, and first of a kind, second-order rate coefficients are reported for the transient radical-induced reduction of Bk(III) and Cf(III) by the hydrated electron (eaq−) and hydrogen atom (H•), demonstrating significant reactivity (up to 1011M-1s-1) indicative of a preference of these metals to adopt divalent states. Additionally, we reportthe first-ever second-order rate coefficients for the transient radical-induced oxidation of these elements by reaction with hydroxyl (•OH) and nitrate (NO3•) radicals, which also exhibited fast reactivity (ca. 108 M-1s-1). Transient Cf(II), Cf(IV), and Bk(IV) absorption spectra are also reported. Overall, the presented data highlight the existence of rich, complex, intrinsic late actinide radiation-induced redox chemistry that has the potential to influence the findings of other areas of actinide science.

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

Multiplicity of Th(IV) and U(VI) HEH[EHP] Chelates at Low Temperatures from Concentrated Nitric Acid Extractions

Organophosphorus extractants have been widely investigated for lanthanide recovery from ore and for application in the reprocessing of spent nuclear fuel, such as in Advanced TALSPEAK schemes. Determining the speciation of the extracted metal complex in the organic phase remains a significant challenge. A better understanding of the variability of HEH[EHP]–actinide complexes and the speciation of chelates for tetra- and hexavalent actinides can improve the predictability of actinide phase transfer in such biphasic systems. Here, the extraction of Th(IV) and U(VI) from nitric acid media using HEH[EHP] in heptane is examined. The distribution ratio as a function of nitric acid concentration was quantified using UV–vis spectroscopy, and then the speciation of HEH[EHP]–metal complexes in the organic phase was investigated using Fourier transform infrared (FTIR) spectroscopy and low-temperature 31 P nuclear magnetic resonance (NMR) spectroscopy. In addition to perturbation of the vibrational modes proximal to the phosphonic moiety in HEH[EHP] in the FTIR spectra, the appearance of a nitrate signal was found in the organic phase following extraction from the highest acidity conditions for U(VI). The 31 P NMR spectra of the organic phase at a low temperature (-70 °C) exhibited a surprising number (n) of resonances (n ≥ 7 for Th(IV) and n ≥ 11 for U(VI)), with the distribution between these resonances changing with the initial concentration of nitric acid in the aqueous phase. These results indicate that the compositions of the inner and outer spheres of the extracted actinides in the organic phase are more diverse than initially thought.

31P NMR↗
DOE OSTI2023

Structural Investigation of Technetium Dibutylphosphate Species Using X-ray Absorption Fine Structure Spectroscopy

The speciation of Tc after the extraction of Tc(IV) from H 2 O and 1 M HNO 3 by dibutylphosphoric acid (HDBP) in dodecane has been studied by X-ray absorption fine structure (XAFS) spectroscopy. Results show the formation of dimeric species with Tc 2 O 2 and Tc 2 O units, and the formulas [Tc 2 O 2 (DBP·HDBP) 4 ] (1) and [Tc 2 O(NO 3 ) 2 (DBP) 2 (DBP·HDBP) 2 ] (2) were, respectively, proposed for the species extracted from H 2 O and 1 M HNO 3 . The interatomic Tc–Tc distances found in the Tc 2 O 2 and Tc 2 O units [2.55(3) and 3.57(4) Å, respectively] are similar to the ones found in Tc(IV) dinuclear species. It is likely that the speciation of Tc(IV) in dodecane is due to the extraction of a species with a Tc 2 O unit for (2) and to the redissolution of a Tc(IV)-DBP solid for (1). The XAFS results for (1) and (2) were compared to that obtained for the extraction of Tc(IV) with TBP/HDBP/dodecane from 0.5 M HNO 3 , (3) which highlight the formation of Tc mononuclear nitrate species {i.e. [Tc(NO 3 ) 3 (DBP)] or [Tc(NO 3 ) 2 (DBP·HDBP)]}. These results confirm the importance of the preparation and speciation of the Tc(IV) aqueous solutions prior to extraction and how much this influences and drives the final Tc speciation in organic extraction. Here, these studies outline the complexity of Tc separation chemistry and provide insights into the behavior of Tc during the reprocessing of used nuclear fuel.

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

Modeling Photolytic Decomposition of Energetically Functionalized Dodecanes

The photolytic stability of explosives and energetic functional groups is of importance for those who regularly handle or are exposed to explosives in typical environmental conditions. This study models the photolytic degradation of dodecane substituted with various energetic functional groups: azide, nitro, nitrate ester, and nitramine. For the studied molecules, it was found that excitons localize on the energetic functional group, no matter where they were initially formed, and thus, the predominant degradation pathway involves the degradation of the energetic functional group. The relative trends for both 4 and 8 eV excitation energies followed with what is expected from the relative stability of the energetic functional groups to thermal and sub-shock degradation. The one notable exception was the azide functional group; more work should be done to further understand the photolytic effects on the azide functional group.

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

High-Resolution Photoelectron Spectroscopy of NO3 – Vibrationally Excited Along Its ν3 Mode

The nitrate (NO3) radical has long been the subject of both experimental and theoretical studies due to its complex electronic structure resulting from vibronic interactions between its X̃2A2' and B̃2E' states. In particular, the definite assignment of the fundamental of its degenerate stretching vibration (ν3) is still under debate. Here, we report high-resolution photoelectron spectra of vibrationally pre-excited NO3- using the recently developed IR-cryo-SEVI technique. The anions are excited through infrared (IR) excitation near 1350 cm-1, accessing the ν3 and 2ν3(e') vibrational levels with band centers at 1350.5 and ∼2700 cm-1, respectively. The IR-cryo-SEVI spectrum for 2ν3 pre-excitation shows clear evidence for an intense 321 transition. From the position of this feature (30031 cm-1), the electron affinity of NO3 also determined in this work (31680 cm-1), and the IR excitation energy, we obtain a fundamental frequency of 1051 cm-1 for the ν3 fundamental of the NO3 radical. This assignment and other features in the IR-cryo-SEVI spectra are supported by spectral simulations based on a vibronic Köppel-Domcke-Cederbaum Hamiltonian. The simulations also show that nearly all features in the IR-cryo-SEVI spectra arise because of pseudo-Jahn-Teller coupling between the X̃ and B̃ states of NO3. The results and analysis presented here settle a long-standing controversy regarding the ν3 frequency of NO3.

Anions↗
DOE OSTI2026

Experimental and Multiscale Modeling Insights for Radiation-Driven Neptunium Redox Processes at Elevated Temperatures

Studies of the radiation-driven reactions of actinide elements at elevated temperatures are extremely limited, but important given that radiation heating of used nuclear fuel can affect the radiolytically promoted actinide redox processes occurring in hydroprocessing environments. Under these conditions, the high concentration of nitric acid present makes the reaction of actinides, such as neptunium, with nitric acid radiolysis products significant. Therefore, here we present derivation of the rate coefficients for the reaction of pentavalent neptunium with the nitrate radical at elevated temperature, resulting in Eyring and Arrhenius parameters for this important reaction. Here, we also revisit our previously published multiscale model predictions for radiation-induced neptunium redox chemistry and present an iteration which successfully operates over a wider range of nitric acid concentrations, 0.1–6.0 M.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Evolution of Radicals from the Photolysis of High Ionic Strength Alkaline Nitrite Solutions

Reactive nitrogen species (RNS), along with reactive oxygen species (ROS), are significant products from radiolysis in solution. While much research has been focused on biological systems, these species are also important products in the autoradiolysis that occurs in nuclear waste. In this work, we determine the correlation between solution constituents, particularly nitrite, and radical products in highly alkaline solutions relevant to liquid waste. Because these radicals tend to be very short-lived, we employ spin trapping in conjunction with electron paramagnetic resonance (EPR) to detect them and quantify their production. Most spin traps do not function in these conditions (>1 M NaOH); however, nitroalkanes such as nitromethane will act as spin traps in their aci form, which is dominant at high pH. To restrict the products to those originating from nitrite, we use 280–480 nm UV light to generate radicals, avoiding products from the photolysis of water. Under these circumstances, nitric oxide, nitrite radicals, and hydroxyl radicals are detected, and the trends with the concentration of the constituents of the solutions are tracked. These include nitrite, nitrate, hydroxide, and carbonate. We find that, while the equilibrium shifts with increasing pH from hydroxyl radicals to the more slowly reacting oxide radicals, the production of nitrite radicals does not decrease.

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

Effects of Sodium and Magnesium Ions on the Photochemically Induced Heterogeneous Formation of Manganese Oxides and Their Structural Evolution

Manganese (Mn) oxides are abundant in aquatic and terrestrial environments, where they play significant roles in redox cycling and biological metabolisms. We recently observed that Mn oxides were homogeneously formed during the abiotic oxidation of Mn 2+ (aq) to Mn(IV) by O 2 •– via nitrate photolysis, at a rate comparable to that of biotic Mn oxide formation. On the other hand, for the heterogeneous formation of Mn oxides, the presence of a substrate can alter the required thermodynamic driving force, which may affect their crystalline phases and further influence the oxidative capability of redox cycling in environmental systems. However, little is known about the photochemically induced heterogeneous formation of Mn oxides on substrates. In this study, we investigated the heterogeneous formation of Mn oxides on a quartz substrate in the presence of two environmentally abundant cations, Na + and Mg 2+ . In contrast to homogeneously generated Mn oxides, the heterogeneously formed Mn oxides displayed faster crystalline phase evolutions and morphological changes over time. Additionally, the coexistence of Na + and Mg 2+ ions greatly affected the initial crystalline phases and the phase evolution, as well as the surface morphologies of the Mn oxides. Finally, these discoveries contribute to our understanding of how various Mn oxides form in nature and provide insights into the processes involved in manufacturing specific Mn oxide crystalline structures for engineering applications.

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

Irradiation-enhanced Interactions at UO 2 /Al 2 O 3 /Al Interfaces

Combustion synthesis is used to prepare thin UO 2 films on aluminum alloy substrates. This simple preparation method involves electrospraying uranyl nitrate + acetylacetone + 2-methoxyethanol solution on the substrate, followed by a short annealing at 350 or 550 °C. The irradiation of films with a 40 Ar 2+ ion beam (energy of 1.7 MeV and fluences of 7.7 × 10 16 and 1.3 × 10 17 ions/cm 2 ) is conducted to investigate irradiation-induced restructuring processes. High-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) investigations show that the annealing temperature significantly influences the crystallinity and stability of materials during irradiation. A small amount of Mg in the alloy substrate diffuses into the amorphous Al 2 O 3 interfacial layer between the film and the substrate. Local thermal spikes from the incoming ions facilitate the irradiation-induced mixing of immiscible Al 2 O 3 and UO 2 for the materials prepared at 350 °C. This mass diffusion produces relatively large cavities at the interface. Selective diffusion of a more significant amount of Mg for the materials prepared at 550 °C suppresses the mixing of the Al 2 O 3 interlayer with the film but forms Mg y U 1–y O 2±x solid solutions during irradiation. Local thermal heating triggers the precipitation of a discontinuous crystalline MgO layer close to the film surface. As a result, the enhanced and selective diffusion of Mg into the film makes the materials prepared at 550 °C more robust and mechanically stable than those prepared at 350 °C.

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

Lanthanum-Doped Graphene for Electrocatalytic Reduction of Nitrogen Monoxide

Electrocatalytic conversion of nitrogen oxides is a promising approach to address nitrogen pollution in underground water. Nitrogen oxides, such as nitrate and nitrite, can be reduced to N 2 and NH 3 over an electrocatalyst, with NO as the key intermediate, subsequent reaction of which controls the overall activity and selectivity. Here, we report density functional theory calculations of NO electrocatalytic reduction (NOER) over lanthanum embedded in graphene, through which we show that the localized states in La drive the reaction favorably due to more pronounced molecular adsorption and charge transfer than transition metals such as Co. The free energy profiles are compared between the La-based single-atom catalyst (SAC) and Co-based SAC, for producing N 2 and NH 3 . We find that the La-SAC intensifies the electron transfer to the adsorbed NO, promoting the first protonation step of NO, which is the potential-limiting step on the Co-SAC. Also, an intriguing effect of the water solvent is revealed on the La-SAC. In addition to stabilizing the intermediate species, water molecules that are coordinated with La participate directly in the protonation steps, enhancing the catalyst activity. Furthermore, this study reveals the unique mechanism of NOER over rare-earth-based catalysts, highlighting the potential application of atomically dispersed f-block elements for electrocatalytic reactions.

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

Radiolytic Production of Radical Species in Gibbsite Doped with Iron and Chromium Ions

Gibbsite (aluminum hydroxide, Al(OH) 3 ) nanoparticles, synthesized from aluminum chloride or aluminum nitrate, were doped with metal ions, Cr(III) or Fe(III), and then irradiated with γ rays to determine the effect of the dopants on radiolytic hydrogen (H 2 ) production and radical generation. The addition of Cr(III) and Fe(III) ions at concentrations of 0.5% or 5% decreased the concentration of stable oxygen-centered radicals, with the strongest suppression in Cr(III) doped samples. A decrease in H 2 yields was observed with increasing Cr(III) or Fe(III) concentrations, with the greatest effect observed for the Fe(III)-doped samples. Reduction of the Cr(III) to Cr(II) and Fe(III) to Fe(II) was also observed, probably due to scavenging of radiolytically produced electrons. However, further processes differ for Fe(III)- and Cr(III)-doped systems. Both ions are reduced by the free electrons, leading to a decrease in H 2 production, but they react differently with the oxygen radicals. Cr(III) can be oxidized by oxygen radicals, whereas Fe(III) cannot. Fe(II) can interact with peroxides, possible products of intermediate oxygen oxidation, converting back to Fe(III) and leaving oxygen radicals behind. These oxidation reactions lead to a difference in the observed relative effects on H 2 yields and oxygen radical production between Cr(III)- and Fe(III)-doped gibbsite. In conclusion, the connection between electron scavenging and H 2 production indicates that radiolytically produced electrons are precursors to H 2 .

Anions↗
DOE OSTI2024

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

In this article, the structural dynamics, chemical reactivity, anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO 2 ), and lithium nitrate (LiNO 3 ), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. 2D IR, NMR, and viscosity results show that LiNO 2 exhibits longer correlation times, lower diffusivity, and nearly four times greater viscosity when compared to the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water-ion interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO 2 and LiNO 3 solutions show significantly reduced chemical reactivity with respect to lithium cations coordinating with the methyl thiocyanate when compared to the lithium halide salts.

2D IR↗
DOE OSTI2024

Molecular Mechanisms of Sorbed Ion Effects during Boehmite Particle Aggregation

Classical theories of particle aggregation, such as Derjaguin–Landau–Verwey–Overbeek (DLVO), do not explain recent observations of ion-specific effects or the complex concentration dependence for aggregation. Thus, here, we probe the molecular mechanisms by which selected alkali nitrate ions (Na + , K + , and NO 3 –) influence aggregation of the mineral boehmite (γ-AlOOH) nanoparticles. Nanoparticle aggregation was analyzed using classical molecular dynamics (CMD) simulations coupled with the metadynamics rare event approach for stoichiometric surface terminations of two boehmite crystal faces. Calculated free energy landscapes reveal how electrolyte ions alter aggregation on different crystal faces relative to pure water. Consistent with experimental observations, we find that adding an electrolyte significantly reduces the energy barrier for particle aggregation (~3–4×). However, in this work, we show this is due to the ions disrupting interstitial water networks, and that aggregation between stoichiometric (010) basal–basal surfaces is more favorable than between (001) edge–edge surfaces (~5–6×) due to the higher interfacial water densities on edge surfaces. The interfacial distances in the interlayer between aggregated particles with electrolytes (~5–10 Å) are larger than those in pure water (a few Ångströms). Together, aggregation/disaggregation in salt solutions is predicted to be more reversible due to these lower energy barriers, but there is uncertainty on the magnitudes of the energies that lead to aggregation at the molecular scale. By analyzing the peak water densities of the first monolayer of interstitial water as a proxy for solvent ordering, we find that the extent of solvent ordering likely determines the structures of aggregated states as well as the energy barriers to move between them. Further, the results suggest a path for developing a molecular-level basis to predict the synergies between ions and crystal faces that facilitate aggregation under given solution conditions. Such fundamental understanding could be applied extensively to the aggregation and precipitation utilization in the biological, pharmaceutical, materials design, environmental remediation, and geological regimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗