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At least 19 records

An introduction to the nitrogen dynamics in controlled systems workshop. Life support and nitrogen: NASA's interest in nitrogen cycling

A Workshop on "Nitrogen Dynamics in Controlled Systems" was held September 26-28, 1995 at the Lawrence Berkeley National Laboratory. The meetings were sponsored by the NASA Advanced Life Support program and the Lawrence Berkeley National Laboratory, and hosted by Prof. Lester Packer of the University of California at Berkeley, and of the Lawrence Berkeley National Laboratory. The Workshop participants were asked to: 1. summarize current knowledge on the cycling of nitrogen in closed systems; 2. identify the needs that closed systems may have for specific forms of nitrogen; 3. identify possible ways of generating and maintaining (or avoiding) specific forms and concentrations of nitrogen; 4. compare biological and physical/chemical methods of transforming nitrogen.

NASA Discipline Number 61-60↗

Solar nitrogen - Evidence for a secular increase in the ratio of nitrogen-15 to nitrogen-14

Solar wind nitrogen, implanted in lunar soil samples, exhibits isotopic variations that are related to the time, although not to the duration, of implantation, with earlier samples characterized by lower ratios of nitrogen-15 to nitrogen-14. An increase in the solar nitrogen-15 content during the lifetime of the lunar regolith is probably caused by spallation of oxygen-16 in the surface regions of the sun.-

Kerridge, J. F.↗

Nitrogen derived from Combined Algal Processing supports algae cultivation for biofuels

Algae biomass, a biofuel feedstock with potential to reduce global CO 2 emissions, is currently too expensive Nitrogen, a significant input and life cycle cost, requires research on recycling and additional sources to reduce costs. Integral to nitrogen recycling is the knowledge of actual nitrogen requirements in outdoor ponds, thus data from the Unified Field Studies of the Algae Testbed Public-Private Partnership was analyzed. The data showed that Nannochloropsis oceanica used 14–24 mg/L NH 4 + per harvest cycle for robust growth. Nitrogen recycled directly from the algae conversion process will likely be the primary source of nitrogen for algae cultivation. Harvested algae can be fractionated via Combined Algal Processing (CAP), where algae are pretreated, fermented, and the fuel feedstocks (e. g. ethanol, lipids) are removed leaving a nitrogen rich slurry. Chlorella vulgaris grew robustly in nitrogen-free media supplemented with CAP residues through 4 harvest cycles with no inhibition. The amount of nitrogen as free ammonium available for recycling directly without further processing was insufficient (~4% of total needed), thus the nitrogen fixing bacteria, Azotobacter vinelandii, was investigated as a means for increasing ammonium concentration in CAP residues. This organism was shown to be proficient at growth on sugars liberated from algae biomass during pretreatment and sustained algae growth using A. vinelandii supernatants was also demonstrated. Using Azotobacter to increase ammonium concentrations on-site using an inexpensive biological process to generate the necessary ammonium for outdoor algae cultivation improves sustainability of algae biofuels by avoiding the energy intensive steps of typical ammonium production and transport. Furthermore, these results show that byproducts of algae conversion begin to close nitrogen demand and, with further supplementation by diazotrophic bacteria or protein hydrolysis, may completely replace current energyintensive and costly industrial nitrogen sources offering a path to increased economic feasibility and improved life cycle analysis of algae-based biofuels.

09 BIOMASS FUELS↗

Nitrogen-Fixing Gamma Proteobacteria Azotobacter vinelandii—A Blueprint for Nitrogen-Fixing Plants?

The availability of fixed nitrogen limits overall agricultural crop production worldwide. The so-called modern “green revolution” catalyzed by the widespread application of nitrogenous fertilizer has propelled global population growth. It has led to imbalances in global biogeochemical nitrogen cycling, resulting in a “nitrogen problem” that is growing at a similar trajectory to the “carbon problem”. As a result of the increasing imbalances in nitrogen cycling and additional environmental problems such as soil acidification, there is renewed and increasing interest in increasing the contributions of biological nitrogen fixation to reduce the inputs of nitrogenous fertilizers in agriculture. Interestingly, biological nitrogen fixation, or life’s ability to convert atmospheric dinitrogen to ammonia, is restricted to microbial life and not associated with any known eukaryotes. It is not clear why plants never evolved the ability to fix nitrogen and rather form associations with nitrogen-fixing microorganisms. Perhaps it is because of the large energy demand of the process, the oxygen sensitivity of the enzymatic apparatus, or simply failure to encounter the appropriate selective pressure. Whatever the reason, it is clear that this ability of crop plants, especially cereals, would transform modern agriculture once again. Successfully engineering plants will require creating an oxygen-free niche that can supply ample energy in a tightly regulated manner to minimize energy waste and ensure the ammonia produced is assimilated. Nitrogen-fixing aerobic bacteria can perhaps provide a blueprint for engineering nitrogen-fixing plants. This short review discusses the key features of robust nitrogen fixation in the model nitrogen-fixing aerobe, gamma proteobacteria Azotobacter vinelandii, in the context of the basic requirements for engineering nitrogen-fixing plants.

Microbiology↗

How nitrogen and oxygen shape SRF cavity performance

Nitrogen and oxygen-based surface treatments have revolutionized the performance of superconducting radiofrequency (SRF) cavities, enabling them to reach higher gradients and lower losses. However, the exact mechanisms by which these treatments improve cavity performance remain largely unknown. This work provides new insights into the role of nitrogen and oxygen in SRF cavity performance by using time-of-flight secondary ion mass spectrometry (TOF-SIMS) to precisely quantify the concentrations and depth profiles of these impurities within niobium cutouts. We correlate these impurity profiles with detailed cavity performance measurements, including surface resistance and quality factor, and compare our findings with predictions from BCS theory. The results demonstrate that while both nitrogen and oxygen enhance performance, ten times more oxygen is required to achieve the same reduction in BCS resistance as interstitial nitrogen. We present a potential model in which the observed variation arises from nitrogen's greater effectiveness in trapping hydrogen, thus reducing the formation of niobium hydrides and enhancing superconducting gap.

Hu, Hannah [Chicago U.]↗

Modeling the effect of nitrogen recycling on the erosion and leakage of tungsten impurities from the SAS-VW divertor in DIII-D during nitrogen gas injection

The new SAS-VW divertor in DIII-D has tungsten-coated components to enable the study of tungsten erosion and leakage from a closed, slot-like divertor. A proposed method of actively managing the tungsten impurities is to inject low-Z impurities, such as nitrogen, into the Scrape-off-Layer (SOL) to modify the conditions in the plasma boundary and in turn manipulate both the erosion and subsequent transport of tungsten. Nitrogen injection from the SOL crown has been modeled using SOLPS-ITER to calculate the background plasma including the intrinsic carbon and the injected nitrogen impurities, and subsequently DIVIMP has been used to calculate the tungsten erosion and transport on top of the background plasma solution. This workflow has been used to model scenarios at a variety of nitrogen injection rates with different assumptions about the nitrogen recycling at the target. In the scenario modeled here, an optimal nitrogen injection rate around 3-4 x 10 20 N/s is found to reduce the amount of tungsten reaching the core by a factor of about 2.4. However, when the nitrogen recycling rate at the divertor targets is high, the nitrogen redistributes within the slot leading to increased tungsten sputtering, and the range of injection rates resulting in tungsten mitigation becomes narrower.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Photosynthetic modulation during the diurnal cycle in a unicellular diazotrophic cyanobacterium grown under nitrogen-replete and nitrogen-fixing conditions

Abstract Cyanobacteria are the only oxygenic photosynthetic organisms that can fix nitrogen. In diazotrophic cyanobacteria, the regulation of photosynthesis during the diurnal cycle is hypothesized to be linked with nitrogen fixation and involve the D1 protein isoform PsbA4. The amount of bioavailable nitrogen has a major impact on productivity in aqueous environments. In contrast to low- or nitrogen-fixing (−N) conditions, little data on photosynthetic regulation under nitrogen-replete (+ N) conditions are available. We compared the regulation of photosynthesis under −N and + N conditions during the diurnal cycle in wild type and a psbA4 deletion strain of the unicellular diazotrophic cyanobacterium Cyanothece sp. ATCC 51142. We observed common changes to light harvesting and photosynthetic electron transport during the dark in + N and −N conditions and found that these modifications occur in both diazotrophic and non-diazotrophic cyanobacteria. Nitrogen availability increased PSII titer when cells transitioned from dark to light and promoted growth. Under −N conditions, deletion of PsbA4 modified charge recombination in dark and regulation of PSII titer during dark to light transition. We conclude that darkness impacts the acceptor-side modifications to PSII and photosynthetic electron transport in cyanobacteria independently of the nitrogen-fixing status and the presence of PsbA4.

59 BASIC BIOLOGICAL SCIENCES↗

Nitrogen and dry-matter partitioning in soybean plants during onset of and recovery from nitrogen stress

The study tested the hypothesis that resupplying nitrogen after a period of nitrogen stress leads to restoration of the balance between root and shoot growth and normal functional activity. Nonnodulated soybean plants were grown hydroponically for 14 days with 1.0 mM NO3- in a complete nutrient solution. One set of plants was continued on the complete nutrient solution for 25 days; a second set was given 0.0 mM NO3- for 25 days; and the third set was given 0.0 mM NO3- for 10 days followed by transfer to the complete solution with 1.0 mM NO3- for 15 days. In continuously nitrogen-stressed plants, emergence and expansion of main-stem and branch leaves were severely inhibited as low nitrogen content limited further growth. This was followed by a shift in partitioning of dry matter from the leaves to the roots, resulting in an initial stimulation of root growth and a decreased shoot:root ratio. Reduced nitrogen also was redistributed from the leaves into the stem and roots. When nitrogen stress was relieved, leaf initiation and expansion were renewed. With the restoration of the balance between root and shoot function, the shoot:root ratio and distribution of reduced nitrogen within the plant organs returned to levels similar to those of nonstressed plants.

NASA Discipline Number 61-10↗

Characterization of ferredoxins involved in electron transfer pathways for nitrogen fixation implicates differences in electronic structure in tuning 2[4Fe 4S] Fd activity

Ferredoxins (Fds) are small proteins which shuttle electrons to pathways like biological nitrogen fixation. Physical properties tune the reactivity of Fds with different pathways, but knowledge on how these properties can be manipulated to engineer new electron transfer pathways is lacking. Recently, we showed that an evolved strain of Rhodopseudomonas palustris uses a new electron transfer pathway for nitrogen fixation. This pathway involves a variant of the primary Fd of nitrogen fixation in R. palustris, Fer1, in which threonine at position 11 is substituted for isoleucine (Fer1 T11I ). To understand why this substitution in Fer1 enables more efficient electron transfer, we used in vivo and in vitro methods to characterize Fer1 and Fer1 T11I . Electrochemical characterization revealed both Fer1 and Fer1 T11I have similar redox transitions (–480 mV and – 550 mV), indicating the reduction potential was unaffected despite the proximity of T11 to an iron-sulfur (Fe—S) cluster of Fer1. Additionally, disruption of hydrogen bonding around an Fe—S cluster in Fer1 by substituting threonine with alanine (T11A) or valine (T11V) did not increase nitrogenase activity, indicating that disruption of hydrogen bonding does not explain the difference in activity observed for Fer1 T11I . Electron paramagnetic resonance spectroscopy studies revealed key differences in the electronic structure of Fer1 and Fer1 T11I , which indicate changes to the high spin states and/or spin-spin coupling between the Fe—S clusters of Fer1. Finally, our data implicates these electronic structure differences in facilitating electron flow and sets a foundation for further investigations to understand the connection between these properties and intermolecular electron transfer.

59 BASIC BIOLOGICAL SCIENCES↗

Insights into Sustainable Nitrogen Fixation by Gas-phase Spectroscopic Measurements and Global Modeling of Reaction Intermediates in Humid Nitrogen Plasma

In this article, there is growing interest in reacting molecular nitrogen and water to sustainably synthesize fixed forms of nitrogen such as ammonia. In particular, low-temperature plasmas can activate these relatively inert feedstocks at or near room temperature without a catalyst. However, because of the enhanced reactivity and nonequilibrium chemistry, a diverse range of products is formed, and the underlying reaction mechanisms are exceedingly complex. In this work, we studied a simplified reactor consisting of a gaseous plasma containing controlled mixtures of nitrogen gas and water vapor. Densities of key chemical species such as N, H, OH, NH, and NO were measured by emission and laser-based spectroscopy as a function of the relative humidity. A global model was constructed and the reaction network was validated by comparing calculated species densities with experiments. We discover that N, a key initial intermediate for ammonia, strongly decreases in the presence of water vapor, and as a result, ammonia formation becomes limited at high relative humidity. This decrease is surprisingly not because N itself reacts, but because one of its main sources, an excited molecular nitrogen state, is reacted away. In addition, oxidation pathways for nitrogen, which lead to NO and related products, are found to be favored over reduction pathways because the corresponding reverse reactions are less significant. Together, this understanding helps explain previously reported observations of selectivity toward nitrogen oxides over ammonia, particularly at higher relative humidities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulated Land Allocation, Nitrogen Use, and Nitrogen Loss in the Mississippi Atchafalaya River Basin for Various RFS2 (Renewable Fuel Standard) Policy Scenarios

Total nitrogen leaching rates were calculated over the Mississippi Atchafalaya River Basin (MARB) using an integrated economic-biophysical modeling approach. Land allocation for corn production and total nitrogen application rates were calculated for crop reporting districts using the Biofuel and Environmental Policy Analysis Model (BEPAM) for 5 RFS2 policy scenarios. These were used as input in the Integrated BIosphere Simulator-Agricultural Version (Agro-IBIS) and the Terrestrial Hydrologic Model with Biogeochemistry (THMB) to calculate the nitrogen loss. Land allocation and total nitrogen application simulations were simulated for the period 2016-2030 for 303 crop reporting districts (https://www.nass.usda.gov/Data_and_Statistics/County_Data_Files/Frequently_Asked_Questions/county_list.txt). The final 2030 values are reported here. Both are stored in csv files. Units for land allocation are million ha and nitrogen application are million kg. The nitrogen leaching rates were modeled with a spatial resolution of 5' x 5' using the North American Datum of 1983 projection and stored in NetCDF files. The 30-year average is calculated over the last 30 years of the 45 years being simulated. Leaching rates are calculated in kg-N/ha.

bioenergy crops↗

Prospects and challenges for nitrogen-atom transfer catalysis

Incorporation of nitrogen-based functional groups can profoundly impact the chemical and physical properties of organic small molecules. One-step conversion of C–H bonds to C–N bonds via C–H amination promises to streamline the synthesis of nitrogen-containing compounds. In pursuit of this promise, nitrogen-group transfer (NGT) from metal nitrenes (i.e., ligand supported M–NR complexes) has been the focus of intense research and development. In contrast, potentially complementary nitrogen-atom transfer (NAT) chemistry, in which a terminal metal nitride (i.e., ligand-supported M–N complex) engages with a C–H bond, is undeveloped. While the earliest examples of stoichiometric NAT chemistry were reported 25 years ago, catalytic protocols are only now beginning to emerge. Furthermore, we summarize the current state-of-the-art in NAT chemistry and discuss opportunities and challenges for the development of NAT catalysis as a platform for incorporation of nitrogen into organic small molecules. Specifically, we 1) highlight the synthetic complementarity of NGT and NAT chemistry, 2) discuss critical aspects of nitride electronic structure that dictate the philicity of supported metal atom, 3) examine the characteristic reactivity of metal nitrides towards substrate functionalization reactions, and 4) present emerging strategies and remaining obstacles to harnessing NAT for selective, catalytic nitrogenation of unfunctionalized organic small molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dissecting the metabolic reprogramming of maize root under nitrogen-deficient stress conditions

The growth and development of maize (Zea mays L.) largely depends on its nutrient uptake through the root. Hence, studying its growth, response, and associated metabolic reprogramming to stress conditions is becoming an important research direction. A genome-scale metabolic model (GSM) for the maize root was developed to study its metabolic reprogramming under nitrogen stress conditions. The model was reconstructed based on the available information from KEGG, UniProt, and MaizeCyc. Transcriptomics data derived from the roots of hydroponically grown maize plants were used to incorporate regulatory constraints in the model and simulate nitrogen-non-limiting (N+) and nitrogen-deficient (N-) condition. Model-predicted flux-sum variability analysis achieved 70% accuracy compared with the experimental change of metabolite levels. In addition to predicting important metabolic reprogramming in central carbon, fatty acid, amino acid, and other secondary metabolism, maize root GSM predicted several metabolites (l-methionine, l-asparagine, l-lysine, cholesterol, and l-pipecolate) playing a regulatory role in the root biomass growth. Furthermore, this study revealed eight phosphatidylcholine and phosphatidylglycerol metabolites which, even though not coupled with biomass production, played a key role in the increased biomass production under N-deficient conditions. Overall, the omics-integrated GSM provides a promising tool to facilitate stress condition analysis for maize root and engineer better stress-tolerant maize genotypes.

Plant Sciences↗

Utilization of ammonium as a nitrogen source: effects of ambient acidity on growth and nitrogen accumulation by soybean

Dry matter accumulation of plants utilizing NH4+ as the sole nitrogen source generally is less than that of plants receiving NO3- unless acidity of the root-zone is controlled at a pH of about 6.0. To test the hypothesis that the reduction in growth is a consequence of nitrogen stress within the plant in response to effects of increased acidity during uptake of NH4+ by roots, nonnodulated soybean plants (Glycine max [L.] Merr. cv Ransom) were grown for 24 days in flowing nutrient culture containing 1.0 millimolar NH4+ as the nitrogen source. Acidities of the culture solutions were controlled at pH 6.1, 5.1, and 4.1 +/- 0.1 by automatic additions of 0.01 N H2SO4 or Ca(OH)2. Plants were sampled at intervals of 3 to 4 days for determination of dry matter and nitrogen accumulation. Rates of NH4+ uptake per gram root dry weight were calculated from these data. Net CO2 exchange rates per unit leaf area were measured on attached leaves by infrared gas analysis. When acidity of the culture solution was increased from pH 6.1 to 5.1, dry matter and nitrogen accumulation were reduced by about 40% within 14 days. Net CO2 exchange rates per unit leaf area, however, were not affected, and the decreased growth was associated with a reduction in rates of appearance and expansion of new leaves. The uptake rates of NH4+ per gram root were about 25% lower throughout the 24 days at pH 5.1 than at 6.1. A further increase in solution acidity from pH 5.1 to 4.1 resulted in cessation of net dry matter production and appearance of new leaves within 10 days. Net CO2 exchange rates per unit leaf area declined rapidly until all viable leaves had abscised by 18 days. Uptake rates of NH4+, which were initially about 50% lower at pH 4.1 than at 6.1 continued to decline with time of exposure until net uptake ceased at 10 days. Since these responses also are characteristic of the sequence of responses that occur during onset and progression of a nitrogen stress, they corroborate our hypothesis.

NASA Discipline Number 61-10↗

Assessment of free-living nitrogen fixing microorganisms for commercial nitrogen fixation

Ammonia production by Klebsiella pneumoniae is not economical with present strains and improving nitrogen fixation to its theoretical limits in this organism is not sufficient to achieve economic viability. Because the value of both the hydrogen produced by this organism and the methane value of the carbon source required greatly exceed the value of the ammonia formed, ammonia (fixed nitrogen) should be considered the by-product. The production of hydrogen by KLEBSIELLA or other anaerobic nitrogen fixers should receive additional study, because the activity of nitrogenase offers a significant improvement in hydrogen production. The production of fixed nitrogen in the form of cell mass by Azotobacter is also uneconomical and the methane value of the carbon substrate exceeds the value of the nitrogen fixed. Parametric studies indicate that as efficiencies approach the theoretical limits the economics may become competitive. The use of nif-derepressed microorganisms, particularly blue-green algae, may have significant potential for in situ fertilization in the environment.

Stokes, B. O.↗

An analytical study of nitrogen oxides and carbon monoxide emissions in hydrocarbon combustion with added nitrogen - Preliminary results

The influence of ground-based gas turbine combustor operating conditions and fuel-bound nitrogen (FBN) found in coal-derived liquid fuels on the formation of nitrogen oxides and carbon monoxide is investigated. Analytical predictions of NOx and CO concentrations are obtained for a two-stage, adiabatic, perfectly-stirred reactor operating on a propane-air mixture, with primary equivalence ratios from 0.5 to 1.7, secondary equivalence ratios of 0.5 or 0.7, primary stage residence times from 12 to 20 msec, secondary stage residence times of 1, 2 and 3 msec and fuel nitrogen contents of 0.5, 1.0 and 2.0 wt %. Minimum nitrogen oxide but maximum carbon monoxide formation is obtained at primary zone equivalence ratios between 1.4 and 1.5, with percentage conversion of FBN to NOx decreasing with increased fuel nitrogen content. Additional secondary dilution is observed to reduce final pollutant concentrations, with NOx concentration independent of secondary residence time and CO decreasing with secondary residence time; primary zone residence time is not observed to affect final NOx and CO concentrations significantly. Finally, comparison of computed results with experimental values shows a good semiquantitative agreement.

Bittker, D. A.↗

Regulation of nitrogen uptake and assimilation: Effects of nitrogen source and root-zone and aerial environment on growth and productivity of soybean

The interdependence of root and shoot growth produces a functional equilibrium as described in quantitative terms by numerous authors. It was noted that bean seedlings grown in a constant environment tended to have a constant distribution pattern of dry matter between roots and leaves characteristic of the set of environmental conditions. Disturbing equilibrium resulted in a change in relative growth of roots and leaves until the original ratio was restored. To define a physiological basis for regulation of nitrogen uptake within the balance between root and shoot activities, the authors combined a partioning scheme and a utilization priority assumption in which: (1) all carbon enters the plant through photosynthesis in leaves and all nitrogen enters the plant through active uptake by roots, (2) nitrogen uptake by roots and secretion into the xylem for transport to the shoots are active processes, (3) availability of exogenous nitrogen determines concentration of soluble carbohydrates within the roots, (4) leaves are a source and a sink for carbohydrates, and (5) the requirement for nitrogen by leaf growth is proportionally greater during initiation and early expansion than during later expansion.

Raper, C. David, Jr.↗