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At least 199 records · Page 11

Calcium nitrate: A chemical admixture to inhibit aggregate dissolution and mitigate expansion caused by alkali-silica reaction

Alkali-silica reaction (ASR) is a significant cause of the degradation of concrete structures. ASR results from the dissolution of reactive silicate aggregates and the subsequent formation of damaging, expansive ASR gels. Despite the prevalence of ASR, so far only lithium-based chemical admixtures have been shown to be successful in mitigating its deleterious effects. Herein, dissolved calcium nitrate (Ca(NO 3 ) 2 : CN) is demonstrated to reduce ASR-induced expansion caused by the use of sodium borosilicate (NBS) glass as a model reactive aggregate. The significance of reductions of NBS-glass dissolution and mortar-bar expansion rates is discussed, with special focus on highlighting the mechanism by which calcium nitrate mitigates ASR, i.e., by the inhibition of aggregate dissolution. This study reveals a new and cost-effective pathway to suppress aggregate dissolution and ASR in concrete based on the dosage of soluble alkaline-earth additives.

36 MATERIALS SCIENCE↗

Zero Valent Iron for Reductive Removal of Technetium-99 from Aqueous Sulfate Solutions - 20347

This research investigates the reductive removal of technetium-99 ({sup 99}Tc) by zero valent iron (ZVI) from low activity waste (LAW) off-gas condensate simulant as a secondary treatment after recovery from vitrification planned at the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Due to its high volatility, only a fraction of Tc{sup (VII)} will be incorporated into glass waste forms. Volatilized Tc will be captured by an off-gas treatment system with current plans to recycle off-gas condensate back to the vitrification facility. The scheme with off-gas recycling will increase Tc loading in the glass waste, but will also increase the concentrations of sulfate, halides, and other problematic constituents impeding overall LAW processing and increasing volume of the glass product. This study focuses on Tc{sup (VII)} removal by ZVI as a feasible pathway to minimize off-gas condensate recycling, which may result in a reduction in the volumes of LAW waste to be immobilized and subsequent cost savings. ZVI is an established treatment agent for redox-active contaminants such as trichloroethylene, nitrate, arsenic, chromium, phenol, and others. It is a commercially available and cost-effective material. Our previous experiments showed that ZVI is very efficient for the reductive removal of {sup 99}Tc. In this work we studied ZVI oxidation under aerobic conditions at pH 7 with 0.1 M Na{sub 2}SO{sub 4} solution (ionic strength, IS, 0.3 M) in the presence and absence of {sup 99}Tc. The concentration of {sup 99}Tc and the changes in pH, dissolved oxygen (DO), and oxidation-reduction potential (ORP) of the simulated solutions were monitored over 8 days. The formation of iron oxide phases was probed by X-ray diffraction (XRD). Obtained results suggest that ZVI contact time with {sup 99}Tc containing solutions for 6 hours resulted in nearly complete removal of {sup 99}Tc from the aqueous phase. XRD analysis showed that the oxidation of ZVI is rapid with formation of magnetite (Fe{sub 3}O{sub 4}) with minor percentage of goethite and maghemite. This work is a part of a larger set of studies investigating the feasibility of {sup 99}Tc reductive removal from the LAW off-gas condensate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Re-Designing the CSP Thermal Energy Storage System to Enable Higher-Temperature Performance at Reduced Cost (Final Technical Report)

Current commercial concentrating solar power (CSP) plants distinguish themselves from ordinary photovoltaic (PV) power plants by storing enough collected energy to enable generation for several hours after the sun goes down. CSP plants store this energy in the sensible heat of nitrate salts in large metallic storage tanks. Stainless-steel AISI 347H (SS347H) is needed for the hot tank operating at about 565 degrees C whereas carbon steel is sufficient for the cold-tank materials. Two-tank nitrate-salt thermal energy storage (TES) is presently in use in several trough-based CSP plants in Europe and in the U.S., operating up to about 390 degrees C. Three commercially operating tower-based CSP plants - Gemasolar in Spain, Crescent Dunes in Nevada, and Noor III in Morocco - use the same approach, storing nitrate salts at temperatures up to 580 degrees C. SS347H is many times more expensive than carbon steel and constitutes a significant cost element in today's CSP plants. Hence, CSP developers need to close the cost gap with PV-based solar plants by making cost reductions in every system of the plant. Redesigning the TES tanks is one opportunity for cost reduction.

14 SOLAR ENERGY↗

Stratospheric ozone decrease due to chlorofluoromethane photolysis - Predictions of latitude dependence

A two-dimensional model is used to predict the 1990 reduction in ozone due to the chlorine compounds formed by chlorofluoromethane (CFM) photolysis when the CFM release rate is held constant at the 1975 value. The predicted globally averaged ozone reduction of 3.5% is similar to that predicted by one-dimensional models that did not include chlorine nitrate chemistry, and used lower values for the reactions rates of NO + HO2 yielding NO2 + OH and O3 + HO2 yielding OH + 2O2. When the 5.7 ppbv increase in chlorine compounds predicted by one-dimensional models to occur under steady-state conditions is simulated by the two-dimensional model, a 26% decrease in atmospheric ozone is predicted. The latitude dependence of the ozone reduction is discussed in terms of the relevant photochemical reaction and transport. The chemical reactions that most strongly influence the meridional dependence of the ozone depletion are identified as those associated with the reactions of chlorine monoxide and atomic oxygen, the recombination of ozone and atomic oxygen, and the photodissociation of molecular oxygen.

Borucki, W. J.↗

Gamma Radiation-Induced Degradation of Acetohydroxamic Acid (AHA) in Aqueous Nitrate and Nitric Acid Solutions Evaluated by Multiscale Modelling

Acetohydroxamic acid (AHA) has been proposed for inclusion in advanced, single-cycle, used nuclear fuel reprocessing solvent systems for the reduction and complexation of plutonium and neptunium ions. For this application, a detailed description of the degradation of AHA in dilute aqueous nitric acid is required. To this end, we present a comprehensive, multiscale computer model for the coupled radiolytic and hydrolytic degradation of AHA in aqueous sodium nitrate and nitric acid solutions. Rate coefficients for the reactions of AHA and HA with the oxidizing nitrate radical were measured for the first time using pulsed electron radiolysis and used as inputs in the kinetic model. The computer model results are validated by comparison to experimental data from steady state gamma irradiations, for which the agreement is excellent. Here, the presented model accurately predicts the yields of the major degradation products of AHA: acetic acid, hydroxylamine, nitrous oxide, and molecular hydrogen.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Editorial: Selective Controls on Microbial Energy Metabolisms: From the Microscale to the Macroscale

A mechanistic and predictive understanding of the genotypic and phenotypic controls on microbial element cycling remains a grand challenge in microbiology. While the composition and concentration of carbon sources, electron donors, and electron acceptors are known to influence microbial community structure by selecting for microbial sub-populations with distinct catabolic and respiratory pathways, selective inhibitors and trace nutrient availability modulate the activity of metabolic enzymes. This in turn influences the distribution of microbial sub-populations with distinct metabolic and respiratory traits, which are then structured by complex multi-dimensional environmental gradients that influence the composition, gene content and element cycling activity of microbiomes. While some parameters are known to select for different respiratory activities (e.g., lanthanides as essential nutrients for methanotrophs, molybdate as a specific inhibitor of sulfate reduction, carbon:nitrogen ratio and concentration as a control on the end-products of nitrate respiration), there are others to discover, and demonstrating how selective parameters operate and mediate element cycling across scales requires multi-disciplinary research in both the lab and field.

59 BASIC BIOLOGICAL SCIENCES↗

Identification of Critical Material Attributes in Lignin Streams Based on Pseudomonas putida Performance

Variability in chemical composition of corn stover feedstocks has been suggested to play a role in biocatalyst performance during the conversion of lignocellulosic biomass to value-added compounds. In previous studies, we investigated the performance of Pseudomonas putida CJ781 - an engineered bacterium that converts aromatic compounds to muconate - on various lignin streams produced from the deacetylation of corn stover, and we found significant differences on muconate production. To better understand the origin of these differences, we down selected twenty-two compounds from literature - that had previously been detected as extractives in lignin streams - and we analyzed their concentrations in 12 lignin streams generated from different feedstocks. P. putida CJ781 was then cultivated in mock lignin streams supplemented with various concentrations of these compounds. Bacterial growth was tracked in microtiter plates and the performance was measured by comparing maximum growth rates among conditions. At maximum concentrations that may be found in lignin streams, sodium was the material attribute that limited growth rate in a greater extent, with a reduction in growth rate by 8 to 37%, depending on the counter ion, with sodium nitrate being the most inhibitory, followed by sodium acetate, sodium chloride, and sodium sulfate. Ammonium acetate was also found to be inhibitory at average concentrations of ammonium in lignin streams, reducing maximum growth rate by 18%. Overall, the data from this study has allowed to down select critical material attributes in lignin streams and process parameters that significantly affect the performance of P. putida and will be used as input to predictive models that aim to reduce risks attributed to feedstock variability in lignocellulosic biorefineries.

biocatalyst↗

Multiscale Modeling of Plutonium Radiation Chemistry in Nitric Acid Solutions. 1. Cobalt-60 Gamma Irradiation of Pu(IV)

We report careful manipulation of the plutonium oxidation states is essential in the study and utilization of its rich redox chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. To this end, we have developed an experimentally evaluated multiscale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M). Under these acidic, aqueous solution conditions, cobalt-60 gamma irradiation afforded marginal net conversion of Pu(IV) to Pu(VI), the extent of which was dependent on the concentration of HNO 3 and absorbed gamma dose. Multiscale calculations, which are in excellent agreement with experimental data, indicate that this observation is due to a combination of inherent plutonium disproportionation reactions and several radiation-induced processes, including redox cycling between Pu(IV) and Pu(III), as achieved by the reduction of Pu(IV) by nitrous acid and hydrogen peroxide, the oxidation of Pu(III) by nitrate and hydroxyl radicals, and the sequential oxidation of Pu(IV) to Pu(V) and Pu(VI) by the remaining available yield of nitrate radicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Frequency Monitoring and Nitrate Sourcing Reveals Baseflow and Stormflow Controls on Total Dissolved Nitrogen and Carbon Export Along a Rural‐Urban Gradient

Abstract Efforts to reduce nitrogen and carbon loading from developed watersheds typically target specific flows or sources, but across gradients in development intensity there is no consensus on the contribution of different flows to total loading or sources of nitrogen export. This information is vital to optimize management strategies leveraging source reductions, stormwater controls, and restorations. We investigate how solute loading and sources vary across flows and land‐use using high frequency monitoring and stable nitrate isotope analysis from five catchments with different sanitary infrastructure, along a gradient in development intensity. High frequency monitoring allowed estimation of annual loading and attribution to storm versus baseflows. Nitrate loads were 16 kg/km 2 /yr. from the forested catchment and ranged from 68 to 119 kg/km 2 /yr., across developed catchments, highest for the septic served site. Across developed catchments, baseflow contributions ranged from 40% of N loading to 75% from the septic served catchment, and the contribution from high stormflows increased with development intensity. Stormflows mobilized and mixed many surface and subsurface nitrate sources while baseflow nitrate was dominated by fewer sources which varied by catchment (soil, wastewater, or fertilizer). To help inform future sampling designs, we demonstrate that grab sampling and targeted storm sampling would likely fail to accurately predict annual loadings within the study period. The dominant baseflow loads and subsurface stormflows are not treated by surface water management practices primarily targeted to surface stormflows. Using a balance of green and gray infrastructure and stream/riparian restoration may target specific flow paths and improve management.

Delesantro, Joseph M.↗

Investigation of the NO reduction by CO reaction over oxidized and reduced NiO x /CeO 2 catalysts

CeO 2 -supported NiO x catalysts have been widely studied in various catalytic reactions including NO reduction by CO. This work is mainly focused on investigation of the impact of catalyst synthesis conditions (e.g., oxidation and reduction) on the physicochemical properties of NiO x /CeO 2 catalysts and the catalytic response for the NO reduction by CO reaction. The oxide NiO x /CeO 2 sample was prepared by an incipient wetness impregnation (IWI) method and reduced under hydrogen reduction treatment at high temperatures (500 and 700 °C). The physicochemical properties of the synthesized samples were characterized by BET analysis, Raman spectroscopy, XRD, XPS, EELS and high-resolution transmission electron microscopy (HR-TEM). The results showed that higher reduction temperature led to the decrease in specific surface area (SSA), fewer oxygen vacancy/defect site, larger crystallite size of the CeO 2 support, and formation of metallic Ni on the surface. The oxidized NiO x /CeO 2 catalyst showed the highest catalytic activity, indicating that the presence of oxygen vacancy/defect sites, Ni 2+ oxidation state, and smaller crystallite size are believed to enhance the catalytic activity. In situ DRIFTS confirmed the generation of several intermediate species, such as nitrate, carbonate, and N 2 O. Finally, on the basis of in situ DRIFTS and activity results, the possible reaction mechanism of NO reduction by CO over NiO x /CeO 2 was proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The enzymes associated with denitrification

The enzymes involved in the reduction of nitrogenous oxides are thought to be intermediates in denitrification processes. This review examines the roles of nitrate reductase, nitrite reductases, nitric oxide reductase, mechanisms of N-N bond formation, and nitrous oxide reductases.

NASA Discipline Exobiology↗

Thermococcus thioreducens sp. nov., a Novel Hyperthermophilic, Obligately Sulfur-Reducing Archaeon from a Deep-Sea Hydrothermal Vent

A hyperthermophilic, sulfur-reducing, organo-heterotrophic archaeon, strain OGL-20P(sup T), was isolated from 'black smoker' chimney material from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge (36.2degN, 33.9degW). The cells of strain OGL-20P(T) have an irregular coccoid shape and are motile with a single flagellum. Growth was observed within a pH range of 5.0-8.5 (optimum pH 7.0), an NaCl concentration range of 1-5%(w/v) (optimum 3%)and a temperature range of 55-94 C (optimum 83-85 C). The novel isolate is strictly anaerobic and obligately dependent upon elemental sulfur as an electron acceptor, but it does not reduce sulfate, sulfite, thiosulfate, Fe(III) or nitrate. Proteolysis products (peptone, bacto-tryptone, Casamino acids and yeast extract) are utilized as substrates during sulfur reduction. Strain OGL-20P(sup T) is resistant to ampicillin, chloram phenicol, kanamycin and gentamicin, but sensitive to tetracycline and rifampicin. The G + C content of the DNA is 52.9 mol% The 16S rRNA gene sequence analysis revealed that strain OGL-20P(sup T) is closely related to Thermococcus coalescens and related species, but no significant homology by DNA-DNA hybridization was observed between those species and the new isolate. On the basis of physiological and molecular properties of the new isolate, we conclude that strain OGL-20P(sup T) represents a new separate species within the genus Thermococcus, for which we propose the name Thermococcus thioreducens sp. nov. The type strain is OGL-20P(sup T) (=JCM 12859(exp T) = DSM 14981(exp T)=ATCC BAA-394(exp T)).

Pikuta, Elena V.↗

Predicting Radiation-Induced Plutonium Redox Chemistry using Multi-scale Modeling Methods

Over the the last 70 years plutonium (Pu) has been integral in the development of several technologies that have changed the world, yet our fundamental understanding of its chemistry is still far from complete. This is a testament to this element’s unique and complex properties, such as its ability to coexist as multiple oxidation states in aqueous solution. Careful manipulation of plutonium oxidation states is essential in the study and utilization of its rich chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. For this reason, we have developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M). Under these acidic, aqueous solution conditions, cobalt-60 gamma irradiation afforded negligible net change in the steady-state oxidation state distribution of Pu(IV). Multi-scale calculations, which are in excellent agreement with experimental data, indicate that this observation is due to radiation-induced redox cycling between Pu(IV) and Pu(III), as achieved by the reduction of Pu(IV) by radiolytic nitrous acid and hydrogen peroxide, and the oxidation of Pu(III) by nitrate and hydroxyl radicals. These radiation-induced redox processes are augmented by plutonium’s inherent disproportionation reactions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Thermococcus Thioreducens sp. Nov., a Novel Hyperthermophilic, Obligately Sulfur-reducing Archaeon from a Deep-sea Hydrothermal Vent

A hyperthermophilic, sulfur-reducing, organo-heterotrophic archaeon, strain OGL-20P was isolated from black smoker chimney material from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge (36.2 N, 33.9 W). The cells of strain OGL-20P(sup T) have an irregular coccoid shape and are motile with a single flagellum. Growth was observed within the pH range 5.0-8.5 (optimum pH 7.0), NaCl concentration range 1-5 % (w/v) (optimum 3%), and temperature range 55-94 C (optimum 83-85 C). The novel isolate is strictly anaerobic and obligately dependent upon elemental sulfur as an electron acceptor, but it does not reduce sulfate, sulfite, thiosulfate, iron (III) or nitrate. Proteolysis products (peptone, bacto-tryptone, casamino-acids, and yeast extract) are utilized as substrates during sulfur-reduction. Strain OGL-20P(sup T) is resistant to ampicillin, chloramphenicol, kanamycin, and gentamycin, but sensitive to tetracycline and rifampicin. The G+C content of DNA is 52.9 mol%. The 16S rRNA gene sequence analysis revealed that strain OGL-20P(sup T) is closely related to Thermococcus coalescens and related species, but no significant homology by DNA-DNA hybridization was observed between those species and the new isolate. On the basis of physiological and molecular properties of the new isolate, we conclude that strain OGL-20P(sup T) represents a new separate species within the genus Thermococcus, and propose the name Thermococcus thioreducens sp. nov. The type strain is OGL-20P(sup T) (= ATCC BAA-394(sup T) = JCM 12859(sup T) = DSM 14981(sup T)).

Pikuta, Elena V.↗

The Influence of Microstructure on TCR for Inkjet-Printed Resistive Temperature Detectors Fabricated Using AgNO 3 /Ethylene-Glycol-Based Inks

This study investigated the influence of microstructure on the performance of Ag inkjet-printed, resistive temperature detectors (RTDs) fabricated using particle-free inks based on a silver nitrate (AgNO 3 ) precursor and ethylene glycol as the ink solvent. Specifically, the temperature coefficient of resistance (TCR) and sensitivity for sensors printed using inks that use monoethylene glycol (mono-EG), diethylene glycol (di-EG), and triethylene glycol (tri-EG) and subjected to a low-pressure argon (Ar) plasma after printing were investigated. Scanning electron microscopy (SEM) confirmed previous findings that microstructure is strongly influenced by the ink solvent, with mono-EG inks producing dense structures, while di- and tri-EG inks produce porous structures, with tri-EG inks yielding the most porous structures. RTD testing revealed that sensors printed using mono-EG ink exhibited the highest TCR (1.7 × 10 -3 /°C), followed by di-EG ink (8.2 × 10 -4 /°C) and tri-EG ink (7.2 × 10 -4 /°C). These findings indicate that porosity exhibits a strong negative influence on TCR. Sensitivity was not strongly influenced by microstructure but rather by the resistance of RTD. The highest sensitivity (0.84 Ω/°C) was observed for an RTD printed using mono-EG ink but not under plasma exposure conditions that yield the highest TCR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boron nitride: Novel ceramic reductant for low‐activity waste vitrification

Abstract During vitrification of radioactive wastes, excessive foaming reduces processing rates within melters by hindering heat transfer from the molten glass pool to the reacting melter feed. Formulations of low‐activity waste (LAW) melter feeds, for vitrification at the Waste Treatment and Immobilization Plant at the Hanford Site, conventionally include the addition of sucrose to mitigate excessive foaming by hastening the denitration process. However, incomplete combustion of sucrose produces organics such as acetonitrile (C 2 H 3 N) that may exceed bounding limits of downstream effluent treatment facilities. Using boron nitride (BN) as an alternate reductant to sucrose, in a representative LAW melter feed reduced C 2 H 3 N production by 90% by preventing the low‐temperature sucrose–nitrate reactions. Furthermore, foaming was suppressed due to the higher decomposition temperature of BN than H 3 BO 3 meaning a delayed reaction of a large fraction of boron with the transient glass‐forming melt until above the foam onset temperature, thus reducing the quantity and viscosity of the connected melt and trapping less gas in the foam layer.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Identifying microbial functional guilds performing cryptic organotrophic and lithotrophic redox cycles in anaerobic granular biofilms

Granular biofilms used in anaerobic digester systems contain diverse microbial populations that interact to hydrolyze organic matter and produce methane within controlled environments. Prior research investigated the feasibility of utilizing granular biofilms obtained from an anaerobic digester to remove nitrate without the addition of exogenous electron donors. These granules possessed a unique structure of alternating light and dark iron sulfide and pyrite rich layers that potentially served as both an electron source and sink, linking carbon, nitrogen, sulfur, and iron cycles. To characterize the functional roles of diverse microbial populations enriched within these layered biofilms, we analyzed metagenomes obtained from three different granules. Comparisons between the functional gene content of forty metagenome assembled genomes (MAGs) identified phylogenetically cohesive functional guilds. Each of these functional MAG clusters was assigned to specific steps in anaerobic digestion (hydrolysis, acidogenesis, acetogenesis, and methanogenesis) and anaerobic respiration (denitrification and sulfate reduction). Comparisons with metagenomes derived from a variety of natural and engineered ecosystems confirmed that the enriched denitrifying bacteria were similar to populations typically found in wetlands and biological nitrogen removal systems. Analysis of read alignments to individual genes within the forty MAGs identified conserved genomic features that were representative of the functions that distinguished functional guilds. Overall, this research illustrates the utility of functional based classification of microorganisms for characterizing ecosystem functions and highlights the potential application of engineered ecosystems to serve as experimental models for complex natural ecosystems.

Ecosystem engineering↗

Direct Synthesis of Ammonia from Nitrate on Amorphous Graphene with Near 100% Efficiency

Abstract Ammonia is an indispensable commodity in the agricultural and pharmaceutical industries. Direct nitrate‐to‐ammonia electroreduction is a decentralized route yet challenged by competing side reactions. Most catalysts are metal‐based, and metal‐free catalysts with high nitrate‐to‐ammonia conversion activity are rarely reported. Herein, it is shown that amorphous graphene synthesized by laser induction and comprising strained and disordered pentagons, hexagons, and heptagons can electrocatalyze the eight‐electron reduction of NO 3 − to NH 3 with a Faradaic efficiency of ≈100% and an ammonia production rate of 2859 µg cm −2 h −1 at −0.93 V versus reversible hydrogen electrode. X‐ray pair‐distribution function analysis and electron microscopy reveal the unique molecular features of amorphous graphene that facilitate NO 3 − reduction. In situ Fourier transform infrared spectroscopy and theoretical calculations establish the critical role of these features in stabilizing the reaction intermediates via structural relaxation. The enhanced catalytic activity enables the implementation of flow electrolysis for the on‐demand synthesis and release of ammonia with >70% selectivity, resulting in significantly increased yields and survival rates when applied to plant cultivation. The results of this study show significant promise for remediating nitrate‐polluted water and completing the NO x cycle.

Huang, Libei↗