Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “nitrite”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Temperature dependence of nitrate-reducing Fe(II) oxidation by Acidovorax strain BoFeN1 – evaluating the role of enzymatic vs. abiotic Fe(II) oxidation by nitrite

ABSTRACT Fe(II) oxidation coupled to nitrate reduction is a widely observed metabolism. However, to what extent the observed Fe(II) oxidation is driven enzymatically or abiotically by metabolically produced nitrite remains puzzling. To distinguish between biotic and abiotic reactions, we cultivated the mixotrophic nitrate-reducing Fe(II)-oxidizing Acidovorax strain BoFeN1 over a wide range of temperatures and compared it to abiotic Fe(II) oxidation by nitrite at temperatures up to 60°C. The collected experimental data were subsequently analyzed through biogeochemical modeling. At 5°C, BoFeN1 cultures consumed acetate and reduced nitrate but did not significantly oxidize Fe(II). Abiotic Fe(II) oxidation by nitrite at different temperatures showed an Arrhenius-type behavior with an activation energy of 80±7 kJ/mol. Above 40°C, the kinetics of Fe(II) oxidation were abiotically driven, whereas at 30°C, where BoFeN1 can actively metabolize, the model-based interpretation strongly suggested that an enzymatic pathway was responsible for a large fraction (ca. 62%) of the oxidation. This result was reproduced even when no additional carbon source was present. Our results show that at below 30°C, i.e. at temperatures representing most natural environments, biological Fe(II) oxidation was largely responsible for overall Fe(II) oxidation, while abiotic Fe(II) oxidation by nitrite played a less important role.

Microbiology↗
DOE OSTI2022

Lewis acid-assisted reduction of nitrite to nitric and nitrous oxides via the elusive nitrite radical dianion

Reduction of nitrite anions (NO 2 - ) to nitric oxide (NO), nitrous oxide (N 2 O) and ultimately dinitrogen (N 2 ) takes place in a variety of environments, including in the soil as part of the biogeochemical nitrogen cycle and in acidified nuclear waste. Nitrite reduction typically takes place within the coordination sphere of a redox-active transition metal. In this report we show that Lewis acid coordination can substantially modify the reduction potential of this polyoxoanion to allow for its reduction under non-aqueous conditions (-0.74 V versus NHE). Detailed characterization confirms the formation of the borane-capped radical nitrite dianion (NO 2 2- ), which features a N(II) oxidation state. Protonation of the nitrite dianion results in the facile loss of nitric oxide (NO), whereas its reaction with NO results in disproportionation to nitrous oxide (N 2 O) and nitrite (NO 2 - ). This system connects three redox levels in the global nitrogen cycle and provides fundamental insights into the conversion of NO 2 - to NO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Elucidating Electron Storage and Distribution within the Pentaheme Scaffold of Cytochrome c Nitrite Reductase (NrfA)

Cytochrome c nitrite reductases (CcNIR or NrfA) play important roles in the global nitrogen cycle by conserving the usable nitrogen in the soil. Here, the electron storage and distribution properties within the pentaheme scaffold of Geobacter lovleyi NrfA were investigated via EPR spectroscopy coupled with chemical titration experiments. Initially, a chemical reduction method was established to sequentially add electrons to the fully oxidized protein, one equivalent at a time. The step–by–step reduction of the hemes was then followed using UV–Vis and EPR spectroscopy. EPR–spectral simulations elucidate the sequence of heme reduction within the pentaheme scaffold, and identify the signals of all five hemes in the EPR spectra. Electrochemical experiments ascertain the reduction potentials for each heme, observed in a narrow +11 (Heme 5) to –212 mV (Heme 3) range (vs SHE). Based on quantitative analysis/simulation of the EPR data, we demonstrate that Hemes 4 and 5 are reduced first (before the active site Heme 1) and serve the purpose of an electron storage unit within the protein. To probe the role of the central Heme 3, a H108M NrfA variant was generated where the reduction potential of Heme 3 is shifted positively (from –212 mV to +29 mV). Here, the H108M mutation significantly impacts the distribution of electrons within the pentaheme scaffold and the reduction potentials of the hemes, reducing the catalytic activity of the enzyme to 3% compared to wild–type. We propose that this is due to Heme 3’s important role as an electron gateway in the wild–type enzyme.

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

Cesium exhibits different mesoscale segregation and ion pairing than lithium, sodium, or potassium in concentrated alkaline aqueous nitrite solutions

Understanding ion pairing in concentrated alkaline electrolytes facilitates the prediction and control of chemical processes in nuclear waste. While sodium is the dominant alkali metal in such systems, cesium often exhibits distinct bulk behavior relative to lighter alkali cations. Aqueous mixtures of cesium hydroxide and sodium nitrite were compared to alkali hydroxide analogs using small-angle x-ray scattering, revealing that cesium disrupts the sodium nitrite electrolyte structure, forming cesium-rich domains. This mesoscale segregation contrasts with the near-ideal mixing observed in other mixed hydroxide–nitrite systems. Raman spectroscopy indicates cesium–nitrite ion pairing, evidenced by vibrational shifts distinct from those associated with sodium. Multinuclear magnetic resonance spectroscopy further supports cesium–nitrite and cesium–hydroxide association, revealing a distinct local environment for nitrite in cesium-containing solutions. Together, these findings show that cesium promotes a unique solution structure dominated by specific ion pairing within segregated domains. This structural organization may influence radical generation pathways in high-ionic-strength alkaline media relevant to nuclear waste processing and management.

Nienhuis, Emily T. [Pacific Northwest National Lab↗
DOE OSTI2021

Sequestration and release of nitrite and nitrate in alkali-activated slag: A route toward smart corrosion control

Intercalating the corrosion inhibitive ions in hydrotalcite is a promising approach to improve the long-term efficiency of inhibitors in corrosion protection of steel in reinforced concrete. In this work, the potential of autogenously generating nitrite- and nitrate-intercalated hydrotalcite in alkali-activated slag (AAS) is investigated. The results show that the added nitrite and nitrate ions are preferably uptaken in the interlayer structure of hydrotalcite in AAS, and the sequestered nitrite and nitrate are released upon chloride exposure in seawater and NaCl solution. The incorporation of nitrite and nitrate has little detrimental effects on the chloride binding capacity of AAS but slightly enhances the chloride ingress due to the pore coarsening effect. Similar to ordinary Portland cement (OPC), AAS is more permeable to the chloride in seawater than NaCl solution. However, unlike the release of bound chloride contributed by ettringite formation in seawater-exposed OPC, the enhanced chloride ingress in seawater-exposed AAS is primarily attributed to the aggravated pH reduction at the exposure front due to brucite formation. This study contributes to the design of alkali-activated binders with a smart inhibitor releasing ability for mitigating corrosion of steel in concrete.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Bacterial nitrite production oxidizes Fe(II) bioremediating acidic abandoned coal mine drainage

Passive remediation systems (PRSs) treating either acidic or neutral abandoned coal mine drainage (AMD) are colonized by bacteria that can bioremediate iron (Fe) through chemical cycling. Due to the low pH in acidic AMD, iron oxidation from soluble Fe(II) to precipitated Fe(III) is mainly directed by microbial oxidation. Less well described are biotic reactions that lead to iron remediation through abiotic secondary reactions. We describe here iron oxidation in acidic AMD that is mediated by the bacterial reduction of nitrate to nitrite followed by the geochemical oxidation of Fe(II). Within an acidic PRS, 4,560 bacteria cultured from the microbial community were screened for their ability to oxidize iron and to perform nitrate-dependent iron oxidation (NDFO). Iron oxidation in the culturable community was observed in every pond of the system, ranging from 2.1% to 11.4%, and NDFO was observed in every pond, ranging from 1.4% to 6.0% of the culturable bacteria. Five NDFO isolates were purified and identified as Paraburkholderia spp. One of our isolates, Paraburkholderia sp. AV18 was shown to drive NDFO through the bacterial production of nitrite that in turn chemically oxidizes Fe(II) (nitrate reduction-iron oxidation; NRIO). AV18 expressed nitrate reductase, napA, concurrent to nitrite production. Burkholderiales are found by 16S rRNA gene sequencing in every pond of the PRS. The frequency of NDFO metabolism in the culturable microbial community and abundance of Burkholderiales in the PRS suggest nitrite producers contribute to the bioremediation of iron in acidic AMD and may be an unharnessed opportunity to increase iron bioremediation in acidic conditions.

(NDFO)↗
DOE OSTI2024

Nitrate and Nitrite at Hanford – From Tanks to Natural Attenuation

Washington River Protection Solutions, LLC (WRPS) contracted Pacific Northwest National Laboratory (PNNL) in support of their maturation testing and analysis to develop and deploy an ambient temperature solidification/stabilization process for low-activity waste (LAW) (referred to as “grout” in this report). The intent of this effort is to support a sample-and-send regulatory and processing strategy in the Hanford 200 West Area, specifically considering grout waste forms disposal at Hanford in the Integrated Disposal Facility (IDF). Currently the disposal of grouted LAW is not an option because the IDF is not permitted to receive this waste form. The material presented in this report is intended to help inform the U.S. Department of Energy (DOE), the site operating contractors, regulatory agencies, and stakeholders of the future implications of IDF disposal of a grouted LAW waste form, specifically for the behavior of nitrate (NO 3 - ) and nitrite (NO 2 - ) at the Hanford. The only calculation of nitrate release from a hypothetical grouted LAW inventory in the IDF showed that the overall release was slightly above the compliance limit of 45 mg/L nitrate and 3.32 mg/L nitrate after 1000 years (Asmussen et al. 2019). As such, uncertainty around the impact of nitrate and nitrite release from the IDF was identified in the recent National Academies of Sciences study of Hanford supplemental LAW by both the national laboratory team and Hanford stakeholders (Bates et al. 2023). However, these calculations (and others for the IDF involving secondary waste grout) may be conservative as no nitrate and nitrite retention in the grout waste form was assumed, nor any attenuation in the subsurface. There is evidence from the literature of processes that can attenuate nitrate migration both in the waste form and in the Hanford subsurface. If found to be technically defensible and likely to occur in the IDF and associated subsurface, then these processes should be included in modeling of the IDF to represent the behavior of nitrate and nitrite more accurately. Doing so would remove unnecessary conservatism in the modeling projections and reduce the uncertainty in assessments of facility compliance of a grouted LAW waste form in the IDF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Nitric Oxide Production from Nitrite plus Ascorbate during Ischemia upon Hippocampal Glutamate NMDA Receptor Stimulation

Nitric oxide (•NO), a diffusible free radical, is an intercellular messenger, playing a crucial role in several key brain physiological processes, including in neurovascular coupling (NVC). In the brain, glutamatergic activation of the neuronal nitric oxide synthase (nNOS) enzyme constitutes its main synthesis pathway. However, when oxygen (O2) supply is compromised, such as in stroke, ischemia, and aging, such •NO production pathway may be seriously impaired. In this context, evidence suggests that, as already observed in the gastric compartment, the reduction of nitrite by dietary compounds (such as ascorbate and polyphenols) or by specific enzymes may occur in the brain, constituting an important rescuing or complementary mechanism of •NO production. Here, using microsensors selective for •NO, we show that nitrite enhanced the •NO production in a concentration-dependent manner and in the presence of ascorbate evoked by N-methyl-D-aspartate (NMDA) and glutamate stimulation of rat hippocampal slices. Additionally, nitrite potentiated the •NO production induced by oxygen-glucose deprivation (OGD). Overall, these observations support the notion of a redox interaction of ascorbate with nitrite yielding •NO upon neuronal glutamatergic activation and given the critical role of NO as the direct mediator of neurovascular coupling may represents a key physiological mechanism by which •NO production for cerebral blood flow (CBF) responses to neuronal activation is sustained under hypoxic/acidic conditions in the brain.

Nunes, Carla (ORCID:0000000274521592)↗
DOE OSTI2021

Autogenous formation and smart behaviors of nitrite- and nitrate-intercalated layered double hydroxides (LDHs) in Portland cement-metakaolin-dolomite blends

In this work, the influence of sodium nitrite (NaNO{sub 2}) and sodium nitrate (NaNO{sub 3}) corrosion inhibitors on the composition, structure, and chloride binding behaviors of layered double hydroxides (LDHs) formed in ternary ordinary Portland cement-metakaolin-dolomite (OPC-MK-DM) systems is studied. The results show that the nitrite and nitrate anions are preferably intercalated in the CaAl LDHs (AFm phases), but not in the MgAl LDHs (hydrotalcite-type phases) due to its limited formation in these ternary cementitious systems cured at ambient temperature. The autogenously formed nitrate- and nitrite-AFm phases are decomposed upon chloride exposure accompanied by Friedel's salts formation, potentially releasing corrosion inhibitive ions to the pore solution in a progressive manner. The NaNO{sub 2} and NaNO{sub 3} incorporation in ternary OPC-MK-DM binders marginally lowers chloride binding capacity but reduces its penetration resistance mainly due to pore coarsening. Nevertheless, a strong linear correlation can be established between the water-soluble and total chloride contents in ternary OPC-MK-DM systems, regardless of OPC replacement level and corrosion inhibitor incorporation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Nitrate and Nitrite Incompatibility with Hydroxide Ions in Concentrated NaOH Solutions: Implications for Hydroxide and Gibbsite Reactivity in Alkaline Nuclear Waste

Electrolyte solutions in alkaline nuclear waste contain aluminate, hydroxide, nitrate and nitrite with sodium as the predominant counterion. The salts of these ions are highly soluble, so the liquids are highly concentrated. This study found that there is a substantial incompatibility between the hydroxide and nitrate and/or nitrate ions. This was determined by the observations that adding just one molal of NaNO2 or NaNO3 to saturated NaOH solution precipitation of 12 moles of NaOH·H2O salt, whereas the common ion effect would have expected only about 1 mole to precipitate. Further analysis indicates that the presence of nitrate and nitrite drastically increases the reactivity of sodium hydroxide ions in solution, which likely influences the reactivity of other hydroxide-mediated reactions. This enhanced reactivity is likely because it disrupts large Na+-OH- ion networks because nitrate and nitrite do not fit in those ion networks similarly to how some ions cannot substitute into a foreign crystal lattice. In contrast, the aluminate ion did not have the same large incompatibility with hydroxide.

Nitrite, Nitrate, Aluminate, NaOH*H2O, Ion-aggrega↗
DOE OSTI2024

Recent mechanistic developments for cytochrome c nitrite reductase, the key enzyme in the dissimilatory nitrate reduction to ammonium pathway

Cytochrome c nitrite reductase, NrfA, is a soluble, periplasmic pentaheme cytochrome responsible for the reduction of nitrite to ammonium in the Dissimilatory Nitrate Reduction to Ammonium (DNRA) pathway, a vital reaction in the global nitrogen cycle. NrfA catalyzes this six-electron and eight-proton reduction of nitrite at a single active site with the help of its quinol oxidase partners. In this study, we summarize the latest progress in elucidating the reaction mechanism of ammonia production, including new findings about the active site architecture of NrfA, as well as recent results that elucidate electron transfer and storage in the pentaheme scaffold of this enzyme.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Photoelectrochemical Nitrate and Nitrite Reduction Using Cu 2 O Photocathodes

Nitrate in wastewater streams causes eutrophication, and nitrate removal is of great importance for environmental protection. Electrochemical nitrate reduction has the advantage of directly converting nitrate to benign or useful chemicals, but it typically requires a considerable overpotential. Here, in this study, photoelectrochemical nitrate reduction is investigated using a Cu 2 O photocathode, where photoexcited electrons in the conduction band inherently have an overpotential of >1.6 V for nitrate reduction. The Cu 2 O photocathode is found to reduce nitrate to nitrite selectively with a high Faradaic efficiency (>85%). More importantly, as the surface of Cu 2 O is particularly catalytic for nitrate reduction, nitrate reduction on Cu 2 O kinetically suppresses photocorrosion of Cu 2 O without the need for additional catalyst or protection layers. In addition to nitrate reduction, nitrite reduction on Cu 2 O is examined to compare the effects of nitrate and nitrite reduction kinetics on the photocurrent generation and photocorrosion of Cu 2 O photocathodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Multinuclear PFGSTE NMR description of 39 K, 23 Na, 7 Li, and 1 H specific activation energies governing diffusion in alkali nitrite solutions

While pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has found widespread use in the quantification of self-diffusivity for many NMR-active nuclei, extending this technique to uncommon nuclei with unfavorable NMR properties remains an active area of research. Potassium-39 ( 39 K) is an archetypical NMR nucleus exhibiting an unfavorable gyromagnetic ratio combined with a very low Larmor frequency. Despite these unfavorable properties, this work demonstrates that 39 K PFGSTE NMR experiments are possible in aqueous solutions of concentrated potassium nitrite. Further, analysis of the results indicates that 39 K NMR diffusometry is feasible when the nuclei exhibit spin–lattice and spin–spin relaxation coefficients on the order of 60–100 ms and 50–100 ms, respectively. The diffusivity of 39 K followed Arrhenius behavior, and comparative 23 Na, 7 Li, and 1 H PFGSTE NMR studies of equimolal sodium nitrite and lithium nitrite solutions led to correlations between the enthalpy of hydration with the activation energy governing self-diffusion of the cations and also of water. Realizing the feasibility of 39 K PFGSTE NMR spectroscopy has a widespread impact across energy sciences because potassium is a common alkali element in energy storage materials and other applications.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Metabolic versatility of the nitrite-oxidizing bacterium Nitrospira marina and its proteomic response to oxygen-limited conditions

The genus Nitrospira is the most widespread group of nitrite-oxidizing bacteria and thrives in diverse natural and engineered ecosystems. Nitrospira marina Nb-295 T was isolated from the ocean over 30 years ago; however, its genome has not yet been analyzed. Here, we investigated the metabolic potential of N. marina based on its complete genome sequence and performed physiological experiments to test genome-derived hypotheses. Our data confirm that N. marina benefits from additions of undefined organic carbon substrates, has adaptations to resist oxidative, osmotic, and UV light-induced stress and low dissolved p CO 2 , and requires exogenous vitamin B 12 . In addition, N. marina is able to grow chemoorganotrophically on formate, and is thus not an obligate chemolithoautotroph. We further investigated the proteomic response of N. marina to low (~5.6 µM) O 2 concentrations. The abundance of a potentially more efficient CO 2 -fixing pyruvate:ferredoxin oxidoreductase (POR) complex and a high-affinity cbb 3 -type terminal oxidase increased under O 2 limitation, suggesting a role in sustaining nitrite oxidation-driven autotrophy. This putatively more O 2 -sensitive POR complex might be protected from oxidative damage by Cu/Zn-binding superoxide dismutase, which also increased in abundance under low O 2 conditions. Furthermore, the upregulation of proteins involved in alternative energy metabolisms, including Group 3b [NiFe] hydrogenase and formate dehydrogenase, indicate a high metabolic versatility to survive conditions unfavorable for aerobic nitrite oxidation. In summary, the genome and proteome of the first marine Nitrospira isolate identifies adaptations to life in the oxic ocean and provides insights into the metabolic diversity and niche differentiation of NOB in marine environments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Adaptive responses of Trichlorobacter lovleyi to nitrite detoxification reveal overlooked contributions of Geobacterales to nitrate ammonification

Abstract Poorly understood microorganisms “short-circuit” the nitrogen cycle via the dissimilatory nitrate reduction to ammonium to retain the element in agricultural lands and stimulate crop productivity. The prevalence of Geobacterales closely related to Trichlorobacter lovleyi in nitrate ammonification hotspots motivated us to investigate adaptive responses contributing to ammonification rates in the laboratory type strain T. lovleyi SZ. Here, we describe the identification of tightly regulated pathways for efficient nitrate foraging and respiration with acetate, an important intermediate of organic matter degradation that Geobacterales efficiently assimilate and oxidize. Challenging the established dogma that high carbon/nitrate ratios stimulate the reduction of nitrate to ammonium, T. lovleyi doubled rapidly across a wide range of ratios provided nitrate concentrations were low enough to prevent the accumulation of the toxic nitrite intermediate. Yet, excess electrons during hydrogenotrophic growth alleviated nitrite toxicity and stimulated the reduction of nitrate to ammonium even under conditions of severe acetate limitation. These findings underscore the importance of nitrite toxicity in the ammonification of nitrate by Geobacterales and provide much needed mechanistic understanding of microbial adaptations contributing to soil nitrogen conservation. This information is critical to enhance the predictive value of genomic-based traits in environmental surveys and to guide strategies for sustainable management of nitrogen fertilization as well as mitigation of green-house emissions and agrochemical leaching from agricultural lands.

Environmental Sciences & Ecology↗
DOE OSTI2024

Refinement of Pitting Factor Basis to Evaluate Minimum Nitrite Requirement in Dilute Waste Chemistries

Considering that chloride concentrations are an order of magnitude lower at SRS than the maximum chloride previously tested to evaluate pitting susceptibility of carbon steel, it has been proposed that the Pitting Factor methodology be refined to determine if a reduction in the minimum nitrite requirement is warranted in more dilute solutions and those with chloride concentrations more indicative of waste tank chemistries at SRS. Through the use of cyclic potentiodynamic polarization, the susceptibility of A537 carbon steel to pitting corrosion was evaluated. The Pitting Factor was shown to accurately predict pitting susceptibility throughout the chemistry envelope evaluated. In addition, it was shown that nitrite is not required for inhibition of pitting corrosion in tank conditions with chloride concentrations observed at SRS and up to 4 M nitrate. Based upon these findings, new control limits were proposed that removed the minimum nitrite requirement within the chemistry envelope evaluated up to 50 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Synthetically Reversible, Proton-Mediated Nitrite N–O Bond Cleavage at a Dicopper Site

A monocationic dicopper(I,I) nitrite complex [Cu 2 (μ-κ 1 :κ 1 -O 2 N)DPFN][NTf 2 ] (2) (DPFN = 2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine, NTf 2 – = N(SO 2 CF 3 ) 2 – ), was synthesized by treatment of a dicopper acetonitrile complex, [Cu 2 (μ-MeCN)DPFN][NTf 2 ] 2 (1), with tetrabutylammonium nitrite ([nBu 4 N][NO 2 ]). DFT calculations indicate that 2 is one of three linkage isomers that are close in energy and presumably accessible in solution. Reaction of the μ-κ 1 :κ 1 -O 2 N complex with p-TolSH produces nitrous acid (HONO) and the corresponding dicopper thiolate species via an acid–base exchange reaction. Notably, treatment of 2 with HNTf 2 results in N–O bond cleavage in the putative, HONO-ligated complex to form the more thermodynamically favorable nitrosyl-bridged dicopper complex [Cu 2 (μ-NO)(μ-OH)DPFN][NTf 2 ] 2 (4). This scission can be reversed via deprotonation of the hydroxy ligand with KO t Bu. X-ray diffraction studies confirmed the solid-state molecular structures of 2 and 4. DFT calculations were used to construct a reaction coordinate diagram detailing formation of the μ-NO complex and to describe its electronic structure. The nitrosyl ligand in 4 is chemically labile, as demonstrated by its ready displacement in reactions with CO or NO 2 – .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗