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At least 19 records

Inhibition of nitrate transport by anti-nitrate reductase IgG fragments and the identification of plasma membrane associated nitrate reductase in roots of barley seedlings

Membrane associated nitrate reductase (NR) was detected in plasma membrane (PM) fractions isolated by aqueous two-phase partitioning from barley (Hordeum vulgare L. var CM 72) roots. The PM associated NR was not removed by washing vesicles with 500 millimolar NaCl and 1 millimolar EDTA and represented up to 4% of the total root NR activity. PM associated NR was stimulated up to 20-fold by Triton X-100 whereas soluble NR was only increased 1.7-fold. The latency was a function of the solubilization of NR from the membrane. NR, solubilized from the PM fraction by Triton X-100 was inactivated by antiserum to Chlorella sorokiniana NR. Anti-NR immunoglobulin G fragments purified from the anti-NR serum inhibited NO3- uptake by more than 90% but had no effect on NO2- uptake. The inhibitory effect was only partially reversible; uptake recovered to 50% of the control after thorough rinsing of roots. Preimmune serum immunoglobulin G fragments inhibited NO3- uptake 36% but the effect was completely reversible by rinsing. Intact NR antiserum had no effect on NO3- uptake. The results present the possibility that NO3- uptake and NO3- reduction in the PM of barley roots may be related.

NASA Discipline Number 61-10

Nitrate transport is independent of NADH and NAD(P)H nitrate reductases in barley seedlings

Barley (Hordeum vulgare L.) has NADH-specific and NAD(P)H-bispecific nitrate reductase isozymes. Four isogenic lines with different nitrate reductase isozyme combinations were used to determine the role of NADH and NAD(P)H nitrate reductases on nitrate transport and assimilation in barley seedlings. Both nitrate reductase isozymes were induced by nitrate and were required for maximum nitrate assimilation in barley seedlings. Genotypes lacking the NADH isozyme (Az12) or the NAD(P)H isozyme (Az70) assimilated 65 or 85%, respectively, as much nitrate as the wild type. Nitrate assimilation by genotype (Az12;Az70) which is deficient in both nitrate reductases, was only 13% of the wild type indicating that the NADH and NAD(P)H nitrate reductase isozymes are responsible for most of the nitrate reduction in barley seedlings. For all genotypes, nitrate assimilation rates in the dark were about 55% of the rates in light. Hypotheses that nitrate reductase has direct or indirect roles in nitrate uptake were not supported by this study. Induction of nitrate transporters and the kinetics of net nitrate uptake were the same for all four genotypes indicating that neither nitrate reductase isozyme has a direct role in nitrate uptake in barley seedlings.

NASA Discipline Number 61-10

Measurement of Peroxyacetyl Nitrate (PAN), Peroxypropionyl Nitrate (PPN) and Peroxymethacryloyl Nitrate (MPAN) during TRACE-P

In Fall 2000, the PANs gas chromatograph (GC) was improved and prepared for installation on the NASA P-3. A number of experiments were conducted in conjunction with the NCAR NO,, instrument (B. Ridley) to settle some of the fine details of the output of the calibration system for each instrument. In addition, the sampling frequency was improved.

Flocke, Frank

Intrinsically Conductive {pi}‑d Conjugated Layers with Co–N4 Active Sites for Efficient Nitrate Electrocatalysis and Zinc-Nitrate Batteries

Electrochemical synthesis of ammonia from nitrate has been extensively investigated as a potential alternative to the energy-intensive Haber-Bosch process. This approach not only operates under ambient conditions but also simultaneously removes nitrate contaminants while producing ammonia as a value-added product. However, the ongoing quest lies in designing an efficient electrocatalyst that achieves a high ammonia yield rate, high selectivity, and long-term stability. Herein, we report the outstanding performance of a Co–N4 coordinated π-d layered Co3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) in nitrate electrocatalysis. The unique combination of abundant Co–N4 active sites and superior electrical conductivity enables significant electrocatalytic activity, delivering a maximum ammonia yield rate of 56.8 mg cm–2 h–1 at −0.8 V vs RHE and a Faradaic efficiency of ∼91% at −0.4 V vs RHE. Mechanistic analysis reveals that alkaline conditions accelerate water dissociation to generate adsorbed hydrogen intermediates (H*), which are utilized by Co–N4 sites to drive the stepwise hydrogenation of nitrate to ammonia while suppressing competing hydrogen evolution reaction (HER) pathways. Furthermore, integration of this catalyst into a zinc-nitrate battery resulted in a maximum power density of 5.3 mW cm–2 and an open-circuit potential of ∼1.45 V. These results highlight the potential of π-d conjugated Co–N4 materials as an efficient catalyst for both environmental remediation and energy conversion.

Namvar, shahrirar

Evidence for a plasma-membrane-bound nitrate reductase involved in nitrate uptake of Chlorella sorokiniana

Anti-nitrate-reductase (NR) immunoglobulin-G (IgG) fragments inhibited nitrate uptake into Chlorella cells but had no affect on nitrate uptake. Intact anti-NR serum and preimmune IgG fragments had no affect on nitrate uptake. Membrane-associated NR was detected in plasma-membrane (PM) fractions isolated by aqueous two-phase partitioning. The PM-associated NR was not removed by sonicating PM vesicles in 500 mM NaCl and 1 mM ethylenediaminetetraacetic acid and represented up to 0.8% of the total Chlorella NR activity. The PM NR was solubilized by Triton X-100 and inactivated by Chlorella NR antiserum. Plasma-membrane NR was present in ammonium-grown Chlorella cells that completely lacked soluble NR activity. The subunit sizes of the PM and soluble NRs were 60 and 95 kDa, respectively, as determined by sodium-dodecyl-sulfate electrophoresis and western blotting.

Non-NASA Center

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Comparative induction of nitrate reductase by nitrate and nitrite in barley leaves

The comparative induction of nitrate reductase (NR) by ambient NO3- and NO2- as a function of influx, reduction (as NR was induced) and accumulation in detached leaves of 8-day-old barley (Hordeum vulgare L.) seedlings was determined. The dynamic interaction of NO3- influx, reduction and accumulation on NR induction was shown. The activity of NR, as it was induced, influenced its further induction by affecting the internal concentration of NO3-. As the ambient concentration of NO3- increased, the relative influences imposed by influx and reduction on NO3- accumulation changed with influx becoming a more predominant regulant. Significant levels of NO3- accumulated in NO2(-)-fed leaves. When the leaves were supplied cycloheximide or tungstate along with NO2-, about 60% more NO3- accumulated in the leaves than in the absence of the inhibitors. In NO3(-)-supplied leaves NR induction was observed at an ambient concentration of as low as 0.02 mM. No NR induction occurred in leaves supplied with NO2- until the ambient NO2- concentration was 0.5 mM. In fact, NR induction from NO2- solutions was not seen until NO3- was detected in the leaves. The amount of NO3- accumulating in NO2(-)-fed leaves induced similar levels of NR as did equivalent amounts of NO3- accumulating from NO3(-)-fed leaves. In all cases the internal concentration of NO3-, but not NO2-, was highly correlated with the amount of NR induced. The evidence indicated that NO3- was a more likely inducer of NR than was NO2-.

NASA Program CELSS

Measurements of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) at selected urban, rural and remote sites

PAN and PPN were measured in a series of eight field studies performed at urban, rural and remote locations in the contiguous U.S. during 1983-1985. Seven of the eight studies were performed in the winter/spring period, a period of sparsely available data. Nearly 2000 air samples were analyzed during these studies. Mean PAN and PPN levels in the range of 45-1600 ppt (max. 7.9 ppb) and 5-230 ppt (max. 0.9 ppb), respectively, were measured. Despite a great deal of observed variability, PAN and PPN showed virtually identical behavior at all sites and in all seasons, supporting the view that these nitrogenous compounds are produced and destroyed by very similar mechanisms. On the average PPN concentrations were about 8 percent (range 3-14 percent) of PAN values. It is inferred that PPN/PAN ratio is highest in urban areas and declines as polluted air masses are transported over long distances.

Singh, Hanwant B.

Atmospheric measurements of peroxyacetyl nitrate and other organic nitrates at high latitudes - Possible sources and sinks

Measurements of PAN and other reactive nitrogen species during the NASA Arctic Boundary Layer Expedition (ABLE 3A) are described, their north-south and east-west gradients in the free troposphere are characterized, and the sources and sinks of PAN and NO(y) are assessed. Large concentrations of PAN and NO(y) are present in the Arctic/sub-Arctic troposphere of the Northern Hemisphere during the summer. Mixing ratios of PAN and a variety of other molecules are more abundant in the free troposphere compared to the boundary layer. Coincident PAN and O3 atmospheric structures suggest that phenomena that define PAN also define the corresponding O3 behavior. Model calculations, correlations between NO(y) and anthropogenic tracers, and the compositions of NO(y) itself suggest that the Arctic/sub-Arctic reactive nitrogen measured during ABLE 3A is predominantly of anthropogenic origin with a minor component from the stratosphere.

Singh, H. B.

In-vivo Raman microspectroscopy reveals differential nitrate concentration in different developmental zones in Arabidopsis roots

Abstract Background Nitrate (NO 3 − ) is one of the two major forms of inorganic nitrogen absorbed by plant roots, and the tissue nitrate concentration in roots is considered important for optimizing developmental programs. Technologies to quantify the expression levels of nitrate transporters and assimilating enzymes at the cellular level have improved drastically in the past decade. However, a technological gap remains for detecting nitrate at a high spatial resolution. Using extraction-based methods, it is challenging to reliably estimate nitrate concentration from a small volume of cells (i.e., with high spatial resolution), since targeting a small or specific group of cells is physically difficult. Alternatively, nitrate detection with microelectrodes offers subcellular resolution with high cell specificity, but this method has some limitations on cell accessibility and detection speed. Finally, optical nitrate biosensors have very good ( in-vivo ) sensitivity (below 1 mM) and cellular-level spatial resolution, but require plant transformation, limiting their applicability. In this work, we apply Raman microspectroscopy for high-dynamic range in-vivo mapping of nitrate in different developmental zones of Arabidopsis thaliana roots in-situ . Results As a proof of concept, we have used Raman microspectroscopy for in-vivo mapping of nitrate content in roots of Arabidopsis seedlings grown on agar media with different nitrate concentrations. Our results revealed that the root nitrate concentration increases gradually from the meristematic zone (~ 250 µm from the root cap) to the maturation zone (~ 3 mm from the root cap) in roots grown under typical growth conditions used for Arabidopsis, a trend that has not been previously reported. This trend was observed for plants grown in agar media with different nitrate concentrations (0.5–10 mM). These results were validated through destructive measurement of nitrate concentration. Conclusions We present a methodology based on Raman microspectroscopy for in-vivo label-free mapping of nitrate within small root tissue volumes in Arabidopsis. Measurements are done in-situ without additional sample preparation. Our measurements revealed nitrate concentration changes from lower to higher concentration from tip to mature root tissue. Accumulation of nitrate in the maturation zone tissue shows a saturation behavior. The presented Raman-based approach allows for in-situ non-destructive measurements of Raman-active compounds.

Fernández González, Alma

Observationally constrained analysis on the distribution of fine- and coarse-mode nitrate in global models

Nitrate plays an important role in the Earth system and air quality. A key challenge in simulating the life cycle of nitrate aerosol in global models is to accurately represent mass size distribution of nitrate aerosol. In this study, we evaluate the performance of the Energy Exascale Earth System Model version 2 (E3SMv2) and the Community Earth System Model version 2 (CESM2), along with Aerosol Comparisons between Observations and Models (AeroCom) phase III models, in simulating spatial distribution of fine-mode nitrate, the mass size distribution of fine- and coarse-mode nitrate, and the gas–aerosol partitioning between nitric acid gas and nitrate, using long-term ground-based observations and measurements from multiple aircraft campaigns. We find that most models underestimate the annual mean PM 2.5 (particulate matter with diameter less than 2.5 µm) nitrate surface concentration averaged over all sites. The observed nitrate PM 2.5 / PM 10 and PM 1 / PM 4 ratios are influenced by the relative contribution of fine sulfate or organic particles and coarse dust or sea salt particles. Overall, the ground-based observations give an annual mean surface nitrate PM 2.5 / PM 10 ratio of 0.7. Most models underestimate the annual mean PM 2.5 / PM 10 ratio in all regions. There are large spreads in the modeled nitrate PM 1 / PM 4 ratios, which span the full range from 0 to 1. Most models underestimate the surface molar ratio of nitrate to total inorganic nitrate averaged across all sites. Our study indicates the importance of gas–aerosol partition parameterization and the simulation of dust and sea salt in correctly simulating the mass size distribution of nitrate.

Nitrate

Longitudinal Patterns in Nitrate Revealed Through Drone‐Based Measurements in an Agriculturally Influenced Midwestern U.S. River

Nitrate concentrations in streams and rivers in the Midwestern United States are often elevated, reflecting the predominance of agriculture in the surrounding landscape. Recent advances in technology, including surface water drones and more precise sensors, provide opportunities to investigate nitrate dynamics with high spatial and temporal resolution. We deployed an aquatic drone, the AquaBOT, in a sixth-order, agriculturally influenced river to examine longitudinal patterns in water quality. Our goal was to measure the spatial and temporal heterogeneity in nitrate and nitrate removal processes and determine the influence of tributary inputs on main stem chemistry. We navigated the drone along a 12-km reach of the Des Moines River (Iowa, USA) nine times between June 2021 and August 2022. Across the deployments, mean nitrate concentration was positively related to discharge and was nearly two orders of magnitude higher in spring than summer. We observed contrasting patterns in main stem nitrate, which decreased downstream during some runs (e.g., 3.1–2.7 mg N L −1 in June 2021), demonstrating net nitrate uptake along the reach, and remained constant on other dates. Similarly, tributaries to the Des Moines had a varied influence on riverine nitrate. Tributaries either increased or decreased main stem nitrate concentrations depending on the tributary and the date. Nitrate removal rates were spatially and temporally variable but showed some consistency at the subreach (2 km) scale, with two subreaches often showing elevated rates of nitrate removal across dates. In conclusion, our study reveals nuanced heterogeneity in nitrate dynamics of the Des Moines River despite the homogeneity of agricultural land cover in the watershed.

54 ENVIRONMENTAL SCIENCES

Nitrates in SNCs: Implications for the nitrogen cycle on Mars

Nitrogen is the second most abundant constituent of the Martian atmosphere, after CO2, present at a level of ca. 2.7 percent. Several authors have hypothesized that earlier in the planet's history, nitrogen was more abundant, but has been removed by processes such as exospheric loss from the atmosphere. However, an alternative sink for atmospheric nitrogen is the regolith; model calculations have predicted that, via the formation of NOx, HNO2 and HNO3 in the lower layers of the Martian atmosphere, the regolith might trap nitrite and nitrate anions, leading to the build-up of involatile nitrates. Integrated over 4.5 x 10(exp 9) yr, such a mechanism would contribute the equivalent of a layer of nitrates up to 0.3 cm thick distributed across the Martian surface. Features in thermal emission spectra of the surface of Mars have been interpreted tentatively as emanating from various anions (carbonates, bicarbonates, sulphates, etc.), and the presence of nitrates has also been addressed as a possibility. The identification of carbonates in SCN meteorites has allowed inferences to be drawn concerning the composition and evolution of the Martian atmosphere in terms of its carbon isotope systematics; if nitrites, nitrates, or other nitrogen-bearing salts could be isolated from SNC's, similar conclusions might be possible for an analogous nitrogen cycle. Nitrates are unstable, being readily soluble in water, and decomposed at temperatures between 50 C and 600 C, depending on composition. Any nitrates present in SNC's might be removed during ejection from the planet's surface, passage to Earth, or during the sample's terrestrial history, by weathering etc. The same might have been said for carbonates, but pockets of shock-produced glass (lithology C) from within the EET A79001 shergottite and bulk samples of other SNC contain this mineral, which did apparently survive. Nitrates occurring within the glassy melt pockets of lithology C in EET A79001 might likewise be protected. Lithology C glass was therefore selected for nitrate analysis, first by non-destructive infra red spectroscopy, and then by stepped combustion.

Grady, Monica M.

Ecological physiology of Synechococcus sp. strain SH-94-5, a naturally occurring cyanobacterium deficient in nitrate assimilation

Synechococcus sp. strain SH-94-5 is a nitrate assimilation-deficient cyanobacterium which was isolated from an ammonium-replete hot spring in central Oregon. While this clone could grow on ammonium and some forms of organic nitrogen as sole nitrogen sources, it could not grow on either nitrate or nitrite, even under conditions favoring passive diffusion. It was determined that this clone does not express functional nitrate reductase or nitrite reductase and that the lack of activity of either enzyme is not due to inactivation of the cyanobacterial nitrogen control protein NtcA. A few other naturally occurring cyanobacterial strains are also nitrate assimilation deficient, and phylogenetic analyses indicated that the ability to utilize nitrate has been independently lost at least four times during the evolutionary history of the cyanobacteria. This phenotype is associated with the presence of environmental ammonium, a negative regulator of nitrate assimilation gene expression, which may indicate that natural selection to maintain functional copies of nitrate assimilation genes has been relaxed in these habitats. These results suggest how the evolutionary fates of conditionally expressed genes might differ between environments and thereby effect ecological divergence and biogeographical structure in the microbial world.

Nitrates/metabolism

Investigation of Global Particulate Nitrate from the AeroCom Phase III Experiment

An assessment of global particulate nitrate and ammonium aerosol based on simulations from nine models participating in the Aerosol Comparisons between Observations and Models (AeroCom) phase III study is presented. A budget analysis was conducted to understand the typical magnitude, distribution, and diversity of the aerosols and their precursors among the models. To gain confidence regarding model performance, the model results were evaluated with various observations globally, including ground station measurements over North America, Europe, and east Asia for tracer concentrations and dry and wet depositions, as well as with aircraft measurements in the Northern Hemisphere mid-to-high latitudes for tracer vertical distributions. Given the unique chemical and physical features of the nitrate occurrence, we further investigated the similarity and differentiation among the models by examining (1) the pH-dependent NH3 wet deposition; (2) the nitrate formation via heterogeneous chemistry on the surface of dust and sea salt particles or thermodynamic equilibrium calculation including dust and sea salt ions; and (3) the nitrate coarse-mode fraction (i.e., coarse/total). It is found that HNO3, which is simulated explicitly based on full O3-HOx-NOx-aerosol chemistry by all models, differs by up to a factor of 9 among the models in its global tropospheric burden. This partially contributes to a large difference in NO3(-), whose atmospheric burden differs by up to a factor of 13. The atmospheric burdens of NH3 and NHC 4 differ by 17 and 4, respectively. Analyses at the process level show that the large diversity in atmospheric burdens of NO3(-), NH3, and NHC4(+) is also related to deposition processes. Wet deposition seems to be the dominant process in determining the diversity in NH3 and NHC 4 lifetimes. It is critical to correctly account for contributions of heterogeneous chemical production of nitrate on dust and sea salt, because this process overwhelmingly controls atmospheric nitrate production (typically greater than 80 %) and determines the coarse- and fine-mode distribution of nitrate aerosol.

Ammonium aerosol based on simulations

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

Antarctic polar stratospheric aerosols: The roles of nitrates, chlorides and sulfates

Nitric and hydrochloric acids have been postulated to condense in the winter polar stratosphere to become an important component of polar stratospheric clouds. One implication is that the removal of NO(y) from the gas phase by this mechanism allows high Cl(x) concentrations to react with O3, because the formation of ClNO3 is inhibited. Contributions of NO3 and Cl to the stratospheric aerosol were determined during the 1987 Airborne Antarctic Ozone Experiment by testing for the presence of nitrates and chlorides in the condensed phase. Aerosol particles were collected on four 500 micron diameter gold wires, each pretreated differently to give results that were specific to certain physical and chemical aerosol properties. One wire was carbon-coated for concentration and size analyses by scanning electron microscopy; X-ray energy dispersive analyses permitted the detection of S and Cl in individual particles. Three more wires were coated with Nitron, barium chloride and silver nitrate, respectively, to detect nitrate, sulfate and chloride in aerosol particles. All three ions, viz., sulfates, nitrates and chlorides were detected in the Antarctic stratospheric aerosol. In terms of number concentrations, the aerosol was dominated by sulfates, followed by chlorides and nitrates. An inverse linear regression can be established between nitrate concentrations and ozone mixing ratio, and between temperature and nitrates.

Pueschel, R. F.