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Effective Potential Energies and Transport Cross Sections for Atom-Molecule Interactions of Nitrogen and Nitrogen

The potential energy surfaces for H2-N and N2-N interactions are calculated by accurate ab initio methods and applied to determine transport data. The results confirm that an effective potential energy for accurately determining transport properties can be calculated using a single orientation. A simple method is developed to determine the dispersion coefficients of effective potential energies Effective potential energies required for O2-O collisions are determ=ined. The H2-N, N2-N, O2-H, and O2-O collision integrals are calculated and tabulated for a large range of temperatures. The theoretical values of the N2-N and O2-O diffusion coefficients compare well with measured data available at room temperature.

Stallcop, James R.↗

Soluble carbohydrate allocation to roots, photosynthetic rate of leaves, and nitrate assimilation as affected by nitrogen stress and irradiance

Upon resupply of exogenous nitrogen to nitrogen-stressed plants, uptake rate of nitrogen is enhanced relative to nonstressed plants. Absorption of nitrogen presumably is dependent on availability of carbohydrates in the roots. A buildup in soluble carbohydrates thus should occur in roots of nitrogen-stressed plants, and upon resupply of exogenous nitrogen the increased uptake rate should be accompanied by a rapid decline in carbohydrates to prestress levels. To evaluate this relationship, three sets of tobacco plants growing in a complete hydroponic solution containing 1.0 mM NO3- were either continued in the complete solution for 21 d, transferred to a minus-nitrogen solution for 21 d, or transferred to a minus-nitrogen solution for 8-9 d and then returned to the 1.0 mM NO3- solution. These nitrogen treatments were imposed upon plants growing at photosynthetic photon flux densities of 700 and 350 micromoles m-2 s-1. Soluble carbohydrate levels in roots increased during onset of nitrogen stress to levels that were fourfold greater than in roots of non-stressed plants. Following resupply of external nitrogen, a rapid resumption of nitrogen uptake was accompanied by a decline in soluble carbohydrates in roots to levels characteristic of nonstressed plants. This pattern of soluble carbohydrate levels in roots during onset of and recovery from nitrogen stress occurred at both irradiance levels. The response of net photosynthetic rate to nitrogen stress could be expressed as a nonlinear function of concentration of reduced nitrogen in leaves. The net photosynthetic rate at a given concentration of reduced nitrogen, however, averaged 10% less at the lower than at the higher irradiance. The decline in net photosynthetic rate per unit of reduced nitrogen in leaves at the lower irradiance was accompanied by an increase in the nitrate fraction of total nitrogen in leaves from 20% at the higher irradiance to 38% at the lower irradiance.

NASA Discipline Number 61-10↗

Solubilities of nitrogen and noble gases in basalt melt

Nitrogen and noble gases are important tracers in geochemistry and chosmochemistry. Compared to noble gases, however, physicochemical properties of nitrogen, such as solubility in melt or melt/silicate partition, are not well known. Solubility of nitrogen in basalt melt depends on redox condition of the atmosphere. For example, solubility of nitrogen in E chondrite melt under reducing conditions is as high as 2 mol percent at 1500 C, suggesting that nitrogen is chemically dissolved in silicate melts, i.e., being dissolved as free anions or replacing oxygen sites in silicate network. However, the solubility and the dissolution mechanism of nitrogen under oxidizing conditions are not well investigated. To obtain nitrogen solubility in silicate melts under various redox conditions and to understand its mechanism, we are conducting experiments by using (15)N(15)N-labeled nitrogen gas. This makes it easy to distinguish dissolved nitrogen from later contamination of atmospheric nitrogen, and hence enables us to measure the nitrogen solubility accurately. As a preliminary experiment, we have measured solubility of nitrogen in basalt melt under the atmospheric oxygen pressure.

Miyazaki, A.↗

Origin and Evolution of Nitrogen on Titan, Enceladus, Triton, and Pluto

Nitrogen, together with carbon, hydrogen, oxygen, phosphorus and sulfur (CHNOPS), plays a central role in life as we know it. Indeed, molecular nitrogen is the most abundant component of the terrestrial atmosphere, and second only to carbon dioxide on Mars and Venus. The Voyager and Cassini-Huygens observations show that copious nitrogen is present on Titan also, comprising some 95% by volume of this moon's 1500 millibar atmosphere. After water vapor, it may be the most abundant (4%) of the gases around tiny Enceladus, as revealed by the recent Cassini observations. A thin nitrogen atmosphere is found even on the coldest of the solar system bodies, Triton and Pluto. The available evidence on nitrogen isotopes and the heavy noble gases suggests that Titan acquired its nitrogen largely in the form of ammonia. Subsequent chemical evolution, beginning with the photolysis of NH3 on primordial Titan, led to the nitrogen atmosphere we see on Titan today. This is also the scenario for the origin of nitrogen on the terrestrial planets. Contrary to Titan, the colder outer solar system objects, Triton and Pluto, neither had the luxury of receiving much arnmonia in the first place, nor of photolyzing whatever little ammonia they did receive in the planetesimals that formed them. On the other hand, it is plausible the planetesimals were capable of trapping and delivering molecular nitrogen directly to Triton and Pluto, unlike Titan. The origin of nitrogen on Enceladus is somewhat enigmatic. A scenario similar to Titan's, but with a role for the interior processes, may be at work. In this paper, we will discuss the source and loss of nitrogen for the above objects, and why Ganymede, the largest moon in the solar system, is nitrogen starved.

Atreya, S. K.↗

Detection and Quantification of Nitrogen Compounds in Martian Solid Samples by the Sample Analysis at Mars (SAM) Instrument Suite

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected both reduced and oxidized nitrogen-bearing compounds during the pyrolysis of surface materials from three sites at Gale Crater. Preliminary detections of nitrogen species include NO, HCN, ClCN, CH3CN, and TFMA (trifluoro-Nmethyl-acetamide). On Earth, nitrogen is a crucial bio-element, and nitrogen availability controls productivity in many environments. Nitrogen has also recently been detected in the form of CN in inclusions in the Martian meteorite Tissint, and isotopically heavy nitrogen (delta N-15 approx +100per mille) has been measured during stepped combustion experiments in several SNC meteorites. The detection of nitrogen-bearing compounds in Martian regolith would have important implications for the habitability of ancient Mars. However, confirmation of indigenous Martian nitrogen bearing compounds will require ruling out their formation from the terrestrial derivatization reagents (e.g. N-methyl-N-tert-butyldimethylsilyl-trifluoroacetamide, MTBSTFA and dimethylformamide, DMF) carried for SAM's wet chemistry experiment that contribute to the SAM background. The nitrogen species we detect in the SAM solid sample analyses can also be produced during laboratory pyrolysis experiments where these reagents are heated in the presence of perchlorate, a compound that has also been identified by SAM in Mars solid samples. However, this does not preclude a Martian origin for some of these compounds, which are present in nanomolar concentrations in SAM evolved gas analyses. Analysis of SAM data and laboratory breadboard tests are underway to determine whether nitrogen species are present at higher concentrations than can be accounted for by maximum estimates of nitrogen contribution from MTBSTFA and DMF. In addition, methods are currently being developed to use GC Column 6, (functionally similar to a commercial Q-Bond column), to separate and identify unretained compounds such as NO, N2O, and NO2, which are difficult to detect by EGA-MS due to mass interferences at 30, 44 and 46, respectively. Here we present evolved gas analysis-mass spectrometry (EGA-MS) and gas chromatography mass spectrometry (GC-MS) data on the identification and quantification of these nitrogen-bearing compounds, and suggestions for their origins

Stern, Jennifer C.↗

Multiple nitrogen components in lunar soil sample 12023

Nitrogen is one of the enigmatic elements in lunar soils and breccias. The large range in (delta)N-15 values found within lunar soils was initially attributed to a secular increase in the N-15/N-14 ratio of 50 percent within the solar corona, and hence in the implanted nitrogen within the lunar regolith. However, more recent explanations have proposed a two (or many) component mixing model of solar wind nitrogen with some hypothetical non-solar components. Such components could include indigenous lunar nitrogen, nitrogen contained in interstellar grains in primitive meteorites, and magnetospheric nitrogen from the terrestrial atmosphere. To understand the makeup of multi-component mixtures it is advantageous to have carbon and noble gas data measured simultaneously, particularly in the case of lunar soils, where the solar wind is a likely fundamental contributor of nitrogen. To this end, a new nitrogen instrument was adapted to give some of the desired data in parallel. Conjoint measurements of N abundance and (delta)N-15 together with N/Ar-36 and Ar-36/Ar-38 ratios obtained during a stepped combustion of lunar soil 12023. The results are preliminary to a much more comprehensive investigation of well characterized fractions of the sample which we still have available from a previous study. Stepped combustion of a sample of 12023,7 yielded 94 ppm nitrogen with a (delta)N-15 = +22.2 percent, as well as the characteristic heavy-light-heavy pattern observed for lunar samples. The low temperature maximum was +75.1 percent at 550 C, the minimum at 800 C with (delta)N-15 = -16.7 percent and the high temperature (delta)N-15 peak is +90.6 percent at 1250 C. The major releases of nitrogen occurred between 650 C - 800 C in the form of a double peak; a third, substantial release occurred at 1150 C yielding 14.2 ppm of nitrogen coinciding with a small but recognizable drop in (delta)N-15 against a regularly increasing trend.

Brilliant, D. R.↗

Onset of and recovery from nitrogen stress during reproductive growth of soybean

Photosynthetic rates and allocation of dry matter, nitrogen, and nonstructural carbohydrates were determined during onset of and recovery from a nitrogen stress for reproductive soybean (Glycine max [L.] Merrill cv Ransom) plants. Until the beginning of seed fill, non-nodulated plants were grown in flowing solution culture with 1.0 mM NO3- in a complete nutrient solution. One set of plants then was transferred to minus-nitrogen solution for 24 d of seed fill; a second set was transferred to a minus-nitrogen solution for 14 d followed by return to the complete solution with 1.0 mM NO3- for the remaining 10 d of seed fill; and a third set was continued on the complete solution. Net CO2 exchange rates of individual leaves, which remained nearly constant during seed fill for nonstressed plants, declined at an accelerated rate during onset of nitrogen stress as the specific content of reduced nitrogen in the leaves was decreased by remobilization of nitrogen to support pod growth. The rate of nitrogen remobilization out of leaves initially was relatively greater than the decrease in photosynthetic rate. While rate of pod growth declined in response to the developing nitrogen stress, photosynthetic assimilation of carbon exceeded reproductive demand and nonstructural carbohydrates accumulated within tissues. Following resupply of exogenous NO3-, specific rate of NO3- uptake by roots was enhanced relative to nonstressed plants. While there was little increase in content of reduced nitrogen in leaves, net remobilization of nitrogen out of leaves ceased, and the decline in photosynthetic rate stabilized at about 51% of that for nonstressed plants. This level of photosynthesis, combined with the availability of elevated pools of carbohydrates accumulated during stress, was sufficient to support the increases in both the specific rates of NO3- uptake and the rate of pod growth during recovery.

Non-NASA Center↗

Nitrogen in Ancient Mud: A Biosignature?

Nitrogen is an essential nutrient for all life on Earth and possibly elsewhere. Burial of nitrogen bound to organic matter constitutes the major flux of nitrogen into sediments today, which has led to the inference that nitrogen enrichments in sedimentary rocks may be a biosignature. However, abiotic processes such as lightning or volcanism can fix atmospheric N2 and contribute to sedimentary nitrogen burial in the absence of life. It is therefore uncertain whether observed nitrogen enrichments of up to 430 ppm in Paleoarchean metasedimentary biotite grains are indeed biogenic. This study seeks to address that problem with a numerical model. The NH4(+) concentration of an abiotic ocean is modeled as a function of source fluxes, pH-dependent NH3 volatilization, and equilibrated adsorption of NH4(+) onto clay particles. The results suggest that the observed nitrogen concentrations in Paleoarchean biotite can only be reconciled with purely abiotic processes if the ocean was more acidic (pH <6) and/or if the source fluxes from lightning and volcanism were at least an order of magnitude higher (≥10(exp 12) mol/yr) than previously thought. The bulk of the nitrogen is thus most likely of biological origin. While this does not necessitate a particular metabolism such as biological N2 fixation, the data provide evidence of nitrogen utilization back to 3.8 Gyr. Nitrogen abundances could thus provide useful information in extraterrestrial missions.

Early Earth↗

The nitrogen cycle: Atmosphere interactions

Atmospheric interactions involving the nitrogen species are varied and complex. These interactions include photochemical reactions, initiated by the absorption of solar photons and chemical kinetic reactions, which involve both homogeneous (gas-to-gas reactions) and heterogeneous (gas-to-particle) reactions. Another important atmospheric interaction is the production of nitrogen oxides by atmospheric lightning. The nitrogen cycle strongly couples the biosphere and atmosphere. Many nitrogen species are produced by biogenic processes. Once in the atmosphere nitrogen oxides are photochemically and chemically transformed to nitrates, which are returned to the biosphere via precipitation, dry deposition and aerosols to close the biosphere-atmosphere nitrogen cycle. The sources, sinks and photochemistry/chemistry of the nitrogen species; atmospheric nitrogen species; souces and sinks of nitrous oxide; sources; sinks and photochemistry/chemistry of ammonia; seasonal variation of the vertical distribution of ammonia in the troposphere; surface and atmospheric sources of the nitrogen species, and seasonal variation of ground level ammonia are summarized.

Levine, J. S.↗

Terrestrial nitrogen cycles: Some unanswered questions

Nitrogen is generally considered to be the element which most often limits the growth of plants in both natural and agricultural ecosystems. It regulates plant growth because photosynthetic rates are strongly dependent on the concentration of nitrogen in leaves, and because relatively large mounts of protein are required for cell division and growth. Yet nitrogen is abundant in the biosphere - the well-mixed pool in the atmosphere is considered inexhaustible compared to biotic demand, and the amount of already fixed organic nitrogen in soils far exceeds annual plant uptake in terrestrial ecosystems. In regions where natural vegetation is not nitrogen limited, continuous cultivation induces nitrogen deficiency. Nitrogen loss from cultivated lands is more rapid than that of other elements, and nitrogen fertilization is generally required to maintain crop yield under any continuous system. The pervasiveness of nitrogen deficiency in many natural and most managed sites is discussed.

Vitousek, P.↗

Are the C delta light nitrogen and noble gases located in the same carrier?

Light nitrogen and the HL family noble gas components of C(sub delta) appear to be separable by high resolution pyrolysis experiments. Thus C(sub delta) is not a homogeneous material and probably consists of debris of many stars. The question of whether the N and Xe(HL) actually reside in different carriers continues to be addressed. It is well known that C(sub delta) which was identified as nanometer sized diamonds contains isotopically anamalous elements, in particular noble gases including Xe(HL) and its family and light nitrogen (delta(N-15) down to -350 percent). Before the true nature of C(sub delta) was recognized, it was easy to suppose that the Xe(HL) and light nitrogen were located in the same carrier. However, recognition that light nitrogen in diamond from different samples varies by greater than a factor of six compared to Xe(HL) fluctuations of ca. 20 percent makes such an assumption questionable. On the basis of simple arithmetic logic, the Xe and nitrogen cannot be absolutely co-located. The average diamond grain consists of only about 1000-2000 atoms of carbon; one grain among a few x 10(exp 6) contains an atom of Xe(HL) while 5-30 atoms of light nitrogen are the typical number which need to be in every diamond grain to account for observed concentrations. If some grains are devoid of N, the others have to have a higher N concentration. Even if we were able to analyze an individual grain of the diamond for noble gases and nitrogen, we would be faced with the monumental task of locating the one amongst 10(exp 6) identical grains containing the Xe atom to examine its nitrogen content. The problem can be simplified to some extent if instead of Xe, He which is 10(exp 4) times more abundant is assumed to be a member of the HL family. Attempts to fractionate the separate carriers might be attempted using He and N as guiding indicators but even experiments of this nature are for the future. Faced with apparently insoluble problems, we have returned to an investigation we last used in our original efforts to find isotopically light nitrogen, that is to compare release patterns of the different components during stepped pyrolysis and combustion.

Verchovsky, A. B.↗

Expansion and photosynthetic rate of leaves of soybean plants during onset of and recovery from nitrogen stress

This study reports on the effects of nitrogen stress and restoration of nitrogen availability after a period of stress on expansion and photosynthetic rate of soybean leaves of differing maturity. We hypothesized that nitrogen resupply would lead to additional accumulation of reduced nitrogen in the leaves and, ultimately, resumption of leaf initiation and expansion and photosynthetic activity. In continuously nitrogen-stressed plants, expansion of middle trifoliolates of main-stem trifoliates and leaf area at full expansion were severely restricted. Leaves showing the greatest effects were initiated after removal of nitrogen. When the reduced nitrogen concentration in mature leaves of continuously stressed plants fell below 9 mg dm-2, the photosynthetic rate per unit leaf decreased rapidly, reaching a minimum of ca. 6-8 mg dm-2 h-1. The older mature leaves tended to abscise at this point, while the youngest leaves remained on the plant and continued to photosynthesize slowly. When nitrogen was resupplied, leaf expansion and final leaf area increased. Leaf initiation was also stimulated as reduced nitrogen levels rose in the leaves. Photosynthetic rates of the oldest and youngest pair of mature leaves returned to values comparable to those of similar-aged leaves of nonstressed soybean plants.

NASA Discipline Number 61-10↗

Ocean Circulation Causes Strong Variability in the Mid-Atlantic Bight Nitrogen Budget

Understanding of nitrogen cycling on continental shelves, a critical component of global nutrient cycling, is hampered by limited observations compared to the strong variability on a wide range of time and space scales. Numerical models have the potential to partially alleviate this issue by filling spatio-temporal data gaps and hence resolving annual area-integrated nutrient fluxes. In this study, a three-dimensional bio geo chemical-circulation model was implemented to simulate the Mid-Atlantic Bight (MAB) nitrogen budget. Model results demonstrate that, on average, MAB net community production (NCP) was positive (plus 0.27 teragrams (Tg) Nitrogen per year), indicating net autotrophy. Inter-annual variability in NCP was strong, with annual values ranging between 0.19 and 0.41 Tg N/year. Along-shelf and across-shelf horizontal transport fluxes were the other dominant terms in the nitrogen budget and were primarily responsible for this NCP variability. The along-shelf current transported nitrogen from the north (0.65 Tg N/year) into the MAB, supplementing the nitrogen entering from terrestrial inputs (0.27 Tg N/year). However, NCP was highest in the year when total water volume transport and inorganic nitrogen input was strongest across the continental slope in the southern MAB, rather than when terrestrial inputs were greatest. Inter-annual variability of NCP appears to be linked to changes in the positions of the Gulf Stream and Slope Water Gyre. Overall, the strong spatio temporal variability of the nitrogen fluxes highlights the importance of observations throughout all seasons and multiple years in order to accurately resolve the current status and future changes of the MAB nitrogen budget.

Friedrichs, Marjorie A. M.↗

Evaluation of a spacecraft nitrogen generator

A method is discussed of generating nitrogen for cabin leakage makeup aboard space vehicles having longer duration missions. The nitrogen generation concept is based on using liquid hydrazine as the stored form of nitrogen to reduce the higher tankage and expendables weight associated with high pressure gaseous or cryogenic liquid nitrogen storage. The hydrazine is catalytically dissociated to yield a mixture of nitrogen and hydrogen. The nitrogen/hydrogen mixture is then separated to yield the makeup nitrogen. The excess supply of hydrogen would be available for use in the reduction of metabolic carbon dioxide. A detailed comparison was completed of Palladium/Silver and Polymer Electrochemical-based Nitrogen Generation Systems. The palladium/silver-based system was judged better than the Polymer Electrochemical Nitrogen Generation System because of lower expendable weight and palladium/silver nitrogen/hydrogen separation represents 'off-the-shelf' technology.

Marshall, R. D.↗