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Open-water wetlands are a novel treatment technology for reverse osmosis concentrate that reduced nitrate concentrations in a pilot-scale system.
The coordination of crystalline products resulting from the co-crystallization of Np(VI), Pu(VI), Am(VI), and Np(V) with uranyl nitrate hexahydrate (UNH) has been revealed through solid-state spectroscopic characterization via diffuse reflectance UV-Vis-NIR spectroscopy, SEM-EDS, and extended X-ray absorption fine structure (EXAFS) spectroscopy. Density functional and multireference wavefunction calculations were performed to analyze the An(VI/V)O 2 (NO 3 ) 2 ·2H 2 O electronic structures and to help assign the observed transitions in the absorption spectra. EXAFS show a similar coordination between the U(VI) in UNH and Np(VI) and Pu(VI); while Am resulted in a similar coordination to Am(III), as reduction of Am(VI) occurred prior to EXAFS data being obtained. Finally, the co-crystallization of the oxidized transuranic species—penta- and hexavalent—with UNH, represents a significant advance from not only a practical standpoint in providing an elegant solution for used nuclear fuel recycle, but also as an avenue to expand the fundamental understanding of the 5f electronic behavior in the solid-state.
The coordination of crystalline products resulting from the co-crystallization of Np(VI), Pu(VI), Am(VI), and Np(V) with uranyl nitrate hexahydrate (UNH) has been revealed through solid-state spectroscopic characterization via diffuse reflectance UV-Vis-NIR, SEM-EDS, and extended X-ray absorption fine structure (EXAFS). Density functional and multireference wavefunction calculations were performed to analyze the An(VI/V)O 2 (NO 3 ) 2 ·2H 2 O electronic structures and to help assign the observed transitions in the absorption spectra. EXAFS show a similar coordination between the U(VI) in UNH and Np(VI) and Pu(VI); while Am resulted in a similar coordination to Am(III), as reduction of Am(VI) occurred prior to EXAFS data being obtained. Here, the co-crystallization of the oxidized transuranic species—penta- and hexavalent—with UNH, represents a significant advance from not only a practical standpoint in providing an elegant solution for used nuclear fuel recycle, but also as an avenue to expand the fundamental understanding of the 5f electronic behavior in the solid-state.
Selective and quantitative measurement of aqueous nitrate (NO 3 – ) anion is achieved using solid [Pt(Cl-4-tpy)Cl]ClO 4 salt (Cl-4-tpy = 4-chloro-2,2':6'2''-terpyridine), and as the salt supported on controlled porous glass. This detection method relies on the color change of the Pt(II) complex from yellow to red and intense luminescence response upon ClO 4 – exchange with NO 3 – due to concomitant enhancement of Pt∙∙∙Pt interactions. Finally, the spectroscopic response is highly selective for NO 3 – over a large range of halides and oxoanions.
The photodetachment spectrum of the nitrate anion (NO 3 ₋ ) in the energy range of the NO 3 second excited state is simulated from first principles using quantum wave packet dynamics. The prediction at 10 K and 435 K relies on the use of an accurate full-dimensional fully coupled five state diabatic potential model utilizing an artificial neural network. The ability of this model to reproduce experimental spectra was demonstrated recently for the lower energy range. Analysis of the spectra indicates a weaker Jahn–Teller coupling compared to the first excited state. The detailed non-adiabatic dynamics is studied by computing the population dynamics. An ultra-fast non-statistical radiationless decay is found only among the Jahn–Teller components, which is followed by a slow statistical non-radiative decay among the different state manifolds. The latter is reproduced perfectly by a simple first order kinetics model. The dynamics in the second excited state is not affected by the presence of a conical intersection with the first excited state manifold.
Electrocatalytic nitrate reduction to ammonia offers a sustainable approach for nitrogenous waste upcycling. This review outlines recent advances in the design of electrocatalysts through cross-scale structural engineering.
The impact of explicit water molecules on the binding of two rare earth nitrate aqua complexes, [X(NO 3 ) 3 (H 2 O) n ] (X = Nd, Yb), has been explored on both the internal pores and external surfaces of MCM-22.
The minireview highlights recent developments in designing electrocatalysts for the co-reduction of CO 2 and nitrates into urea. It also discusses advanced detection methods for intermediates and final products, as well as future research prospects.
This study examines nitrate and nitrite reduction by a tetrapodal iron complex, identifying key intermediates in the reaction via a bimetallic mechanism.
The reaction of a Mn III -hydroxo complex with ceric ammonium nitrate generates a product with a Mn III –O–Ce IV core that has enhanced reactivity in one-electron oxidation reactions and new reactivity in two-electron oxidation reactions.
In highly concentrated electrolyte solutions, where classical models often fail, specific ion–solvent interactions dictate bulk properties. Here, in this study, we combine small-angle X-ray scattering (SAXS) and Raman spectroscopy to link molecular coordination to mesoscale structure across alkali nitrate and nitrite solutions. Our results reveal a structural hierarchy driven by cation identity in that smaller cations (Li + , Na + ) form discrete contact ion pairs, while larger cations (K + , Rb + ) promote increasingly disordered local coordination and extended solute–solvent networks. Using nitrite salts as a structural control, we confirm this organizing principle across different anion geometries. Cs + undergoes a concentration-induced transition to a uniquely ordered state, resulting in a highly structured solution. This work provides a direct, mechanistic explanation for how cation choice dictates the ‘rules’ of solution architecture, offering a predictive basis for understanding phase behavior in complex industrial and environmental systems.
Remote quantification of Pu(VI) (0–5 mol%) co-crystallized with U in uranyl nitrate hexahydrate (UNH) crystals was achieved in a glove box using reflectance spectroscopy coupled with chemometric modeling. Reflectance spectra were also acquired for Pu(IV) and Np(VI) (0–5 mol%) crystallized with UNH; revealing spectral features consistent with their solution-phase analogs. Principal component analysis revealed Pu(IV/VI) and Np(VI) concentrations as the primary source of variation in the data, informing the development of a supervised partial least squares regression model for Pu(VI). The resulting calibration demonstrated robust performance, with replicate root mean square errors near 10% and quantifiable limits near 0.2 mol% Pu(VI) relative to U. The Pu(VI) remained stable in the crystalline UNH matrix for at least one week with minimal reduction to Pu(IV). Notably, Pu(VI) and Np(VI) incorporation in UNH quenched U(VI) fluorescence while Pu(IV) did not. This study presents a noninvasive, spectroscopic approach for solid-state Pu quantification, with direct implications for material accountability and nuclear nonproliferation monitoring.
The fundamental understanding of intermolecular interactions of ionic liquids (ILs) with water is essential in predicting IL–water thermodynamic properties. In this study, intermolecular or noncovalent interactions were studied for 1,3-dimethyl imidazolium [DMIM]+ cation and nitrate [NO 3 ] – anion with water, employing quantum mechanics and molecular dynamics simulations. Molecular dynamics simulations were performed using a revised multipolar polarizable force field. The effect of water on ionic liquids was evaluated in terms of thermodynamic and dynamic properties. Thermodynamic properties included liquid densities ρ, excess molar volumes ΔV E , and liquid structures g(r). Dynamic properties included self-diffusion coefficients D of mixture constituents as a function of water concentration. The density of ionic liquid–water mixtures monotonically decrease with increasing concentration of water. A negative excess volume was obtained for low and high water concentrations, demonstrating strong intermolecular interactions of water with ionic liquid components. Liquid structures of ionic liquid–water mixtures revealed a tendency for anions to interact with cations at shorter intermolecular distances when the water concentration is increased. Diffusion rates were found to increase for all mixture components with increase in the fraction of water. A significant change in the diffusion rate was found at ~0.3 weight fraction of water. However, the water self-diffusion coefficient was dominant at all concentrations. Furthermore, the ratio of water/anion and anion/cation self-diffusion coefficients was found to decrease linearly with increasing concentration of water molecules.
Climate warming is increasing ocean stratification, which in turn should decrease the nutrient flux to the upper ocean. This may slow marine primary productivity, causing cascading effects throughout food webs. However, observing changes in upper ocean nutrients is challenging because surface concentrations are often below detection limits. We show that the nutricline depth, where nutrient concentrations reach well-detected levels, is tied to productivity and upper ocean nutrient availability. Next, we quantify nutricline depths from a global database of observed vertical nitrate and phosphate profiles to assess contemporary trends in global nutrient availability (1972–2022). We find strong evidence that the P-nutricline (phosphacline) is mostly deepening, especially throughout the southern hemisphere, but the N-nutricline (nitracline) remains mostly stable. Earth System Model (ESM) simulations support the hypothesis that reduced iron stress and increased nitrogen fixation buffer the nitracline, but not phosphacline, against increasing stratification. These contemporary trends are expected to continue in the coming decades, leading to increasing phosphorus but not nitrogen stress for marine phytoplankton, with important ramifications for ocean biogeochemistry and food web dynamics.
Nitrogen (N) fixation in cereals by root-associated bacteria is a promising solution for reducing use of chemical N fertilizers in agriculture. However, plant and bacterial responses are unpredictable across environments. We hypothesized that cereal responses to N-fixing bacteria are dynamic, depending on N supply and time. To quantify the dynamics, a gnotobiotic, fabricated ecosystem (EcoFAB) was adapted to analyse N mass balance, to image shoot and root growth, and to measure gene expression of Brachypodium distachyon inoculated with the N-fixing bacterium Herbaspirillum seropedicae. Phenotyping throughput of EcoFAB-N was 25–30 plants h -1 with open software and imaging systems. Herbaspirillum seropedicae inoculation of B. distachyon shifted root and shoot growth, nitrate versus ammonium uptake, and gene expression with time; directions and magnitude depended on N availability. Primary roots were longer and root hairs shorter regardless of N, with stronger changes at low N. At higher N, H. seropedicae provided 11% of the total plant N that came from sources other than the seed or the nutrient solution. The time-resolved phenotypic and molecular data point to distinct modes of action: at 5 mM NH 4 NO 3 the benefit appears through N fixation, while at 0.5 mM NH 4 NO 3 the mechanism appears to be plant physiological, with H. seropedicae promoting uptake of N from the root medium.Future work could fine-tune plant and root-associated microorganisms to growth and nutrient dynamics.
Abstract Laboratory‐based studies on microbial Fe(II) oxidation are commonly performed for 5–10 days in small volumes with high substrate concentrations, resulting in geochemical gradients and volumetric effects caused by sampling. We used a chemostat to enable uninterrupted supply of medium and investigated autotrophic nitrate‐reducing Fe(II)‐oxidizing culture KS for 24 days. We analysed Fe‐ and N‐speciation, cell‐mineral associations, and the identity of minerals. Results were compared to batch systems (50 and 700 mL—static/shaken). The Fe(II) oxidation rate was highest in the chemostat with 7.57 mM Fe(II) d −1 , while the extent of oxidation was similar to the other experimental setups (average oxidation of 92% of all Fe(II)). Short‐range ordered Fe(III) phases, presumably ferrihydrite, precipitated and later goethite was detected in the chemostat. The 1 mM solid phase Fe(II) remained in the chemostat, up to 15 μM of reactive nitrite was measured, and 42% of visualized cells were partially or completely mineral‐encrusted, likely caused by abiotic oxidation of Fe(II) by nitrite. Despite (partial) encrustation, cells were still viable. Our results show that even with similar oxidation rates as in batch cultures, cultivating Fe(II)‐oxidizing microorganisms under continuous conditions reveals the importance of reactive nitrogen intermediates on Fe(II) oxidation, mineral formation and cell–mineral interactions.
Bacillus cereus strain CPT56D-587-MTF was isolated from nitrate- and toxic metal-contaminated subsurface sediment at the Oak Ridge Reservation (ORR) (Oak Ridge, TN, USA). Here, we report the complete genome sequence of this strain to provide genomic insight into its strategies for survival at this mixed-waste site.
ABSTRACT Bacillus sp. strain EB106-08-02-XG196 was isolated from a high-nitrate- and heavy metal-contaminated site at the Oak Ridge Reservation in Tennessee. We report the draft genome sequence of this strain to provide insights into the genomic basis for surviving in this unique environment.