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At least 109 records · Page 6

New soil carbon sequestration with nitrogen enrichment: a meta-analysis

Background and aims: Through agriculture and industry, humans are increasing the deposition and availability of nitrogen (N) in ecosystems worldwide. Carbon (C) isotope tracers provide useful insights into soil C dynamics, as they allow to study soil C pools of different ages. In this study we evaluated to what extent N enrichment affects soil C dynamics in experiments that applied C isotope tracers. Methods: Using meta-analysis, we synthesized data from 35 published papers. We made a distinction between “new C” and “old C” stocks, i.e., soil C derived from plant C input since the start of the isotopic enrichment, or unlabeled, pre-existing soil C. Results: Averaged across studies, N addition increased new soil C stocks (+30.3%), total soil C stocks (+6.1%) and soil C input proxies (+30.7%). Although N addition had no overall, average, effect on old soil C stocks and old soil C respiration, old soil C stocks increased with the amount of N added and respiration of old soil C declined. Nitrogen-induced effects on new soil C and soil C input both decreased with the amount of extraneous N added in control treatments. Conclusion: Although our findings require additional confirmation from long-term field experiments, our analysis provides isotopic evidence that N addition stimulates soil C storage both by increasing soil C input and (at high N rates) by decreasing decomposition of old soil C. Furthermore, we demonstrate that the widely reported saturating response of plant growth to N enrichment also applies to new soil C storage.

54 ENVIRONMENTAL SCIENCES↗

Subsidence of aircraft engine exhaust in the stratosphere: Implications for calculated ozone depletions

The deposition altitude of nitrogen oxides and other exhaust species emitted by stratospheric aircraft is a crucial parameter in determining the impact of these emissions on stratospheric ozone. We have utilized a model for the wake of a High-Speed Civil Transport (HSCT) to estimate the enhancements in water and reductions in ozone in these wakes as a function of time. Radiative calculations indicate differential cooling rates as large as -5K/day at the beginning of the far-wake regime, mostly due to the enhanced water abundance. These cooling rates would imply a net sinking of the wakes of about 1.2 km after three days in the limit of no mixing. Calculated mid-latitude column ozone reductions due to emissions from a Mach 2.4 HSCT would then change from about -1% to -06%. However, more realistic calculations adopting moderate mixing for the wake reduce the net sinking to less than 0.2 km, making the impact of radiative subsidence negligible.

Rodriguez, J. M.↗

Geochemistry and Organic Chemistry on the Surface of Titan

Titan's atmosphere produces a wealth of organic products from methane and nitrogen. These products, deposited on the surface in liquid and solid form, may interact with surface ices and energy sources to produce compounds of exobiological interest. Additional information is contained in the original extended abstract.

Lunine, J. I.↗

The oxidation of titanium films saturated with nitrogen at 300 K

In a two-chamber system designed for physical adsorption studies, a titanium film was deposited and exposed to nitrogen. Oxygen was then admitted into the system. However, the presence of oxygen could not be detected by the mass spectrometer during the first 300 seconds of oxygen admission. On the basis of the data it is assumed that the capture probability of the nitrogen-saturated titanium film for oxygen is very nearly 1. Based on this assumption, the titanium film adsorbed approximately 3 monolayers of oxygen.

Outlaw, R. A.↗

Tetracene Functionalized Si(111) Achieves Enhanced Solar-to-Chemical Energy Conversion via Molecular Acceptor States

The properties of semiconductor|liquid interfaces play a critical role in determining the efficiency of solar-to-hydrogen (STH) conversion. Here, we investigate how molecular functionalization of Si(111) and Si(111)|TiO 2 surfaces impacts photoelectrochemical (PEC) hydrogen production efficiency. We find that functionalization of ∼3% of the atop sites of Si(111) with either 9-anthracene (Anth) or 5-tetracene (Tet), with the remaining sites passivated by methyl groups, provides substrates with high electronic quality and low surface oxide densities, as determined by X-ray photoelectron spectroscopy (XPS) measurements. Surface photovoltage (SPV) spectroscopy shows that surfaces modified with Anth or Tet exhibit an increased photovoltage, with Tet-functionalized surfaces yielding an additional 192 meV relative to methyl-terminated Si(111), indicating improved charge separation for Si-Tet. Further improvement in onset potential was achieved by replacing a nitrogen-containing TiO 2 atomic layer deposition (ALD) precursor (TDMAT) with a precursor lacking nitrogen (TTIP), which eliminates the parasitic defect band in the TiO 2 overlayer (p-Si(111)-Tet|TTIP-TiO 2 |Pt: V OC = +0.283 ± 0.041 V vs RHE). Density functional theory (DFT) analysis demonstrates that compared with Anth-modified Si(111), the Tet-modified surface exhibits more hybridized Si(111)-Tet states closer to the silicon band edges. Mercury contact current–voltage (I–V, dark) measurements quantified the relative interfacial density of states of Si-Tet, Si-Anth and Si-Me surfaces─revealing that the interfacial state density was highest for Si-Tet. This suggests that such hybridized interfaces serve to capture better photoexcited charge, which enables facile electron transfer to molecular acceptors in solution. Altogether, the data indicate that beneficial hybrid molecular LUMO surface states interacting with the Si conduction band edge results in improved hydrogen evolution (HER) performance for p-Si devices.

Group theory↗

Improved refractory coatings

The adhesion, friction and wear properties of sputtered refractory coatings on substrates of materials that form stable nitrides are enhanced by placing each substrate directly below a titanium carbide target of a commercial radiofrequency diode apparatus in a vacuum chamber. Nitrogen is bled into the system through a nozzle resulting in a small partial pressure of about 0.5% to 2.5% during the first two minutes of deposition. The flow of nitrogen is then stopped, and the sputtering ambient is reduced to pure argon through a nozzle without interrupting the sputtering process. When nitrogen is deliberately introduced during the crucial interface formation, some of the titanium at the interface reacts to form titanium nitride while the metal of the substrate also forms the nitride. These two nitrides atomically mixed together in the interfacial region act to more strongly bond the growing titanium carbide coating as it forms on the substrate.

Brainard, W. A.↗

Refractory coatings and method of producing the same

The adhesion, friction, and wear properties of sputtered refractory coatings on substrates of materials that form stable nitrides is improved by placing each substrate directly below a titanium carbide target of a commercial radiofrequency diode apparatus in a vacuum chamber. Nitrogen is bled into the system through a nozzle resulting in a small partial pressure of about 0.5% to 2.5% during the first two minutes of deposition. The flow of nitrogen is then stopped, and the sputtering ambient is reduced to pure argon through a nozzle without interrupting the sputtering process. When nitrogen is deliberately introduced during the crucial interface formation, some of the titanium at the interface reacts to form titanium nitride while the metal of the substrate also forms the nitride. These two nitrides atomically mixed together in the interfacial region act to more strongly bond the growing titanium carbide coating as it forms on the substrate.

Brainard, W. A.↗

Refractory coatings

A thin sputtered film is discussed which exhibits improved adherence to a substrate and has improved friction and wear characteristics. Each substrate is placed directly below a titanium carbide target of a commercial radiofrequency diode apparatus in a vacuum chamber. Nitrogen is bled into the system through a nozzle resulting in a small partial pressure of about 0.5% to 2.5% during the first two minutes of deposition. The flow of nitrogen is then stopped, and the sputtering ambient is reduced to pure argon through a nozzle without interrupting the sputtering process.

Brainard, W. A.↗

Seasonal Nitrogen Cycles on Pluto

A thermal model, developed to predict seasonal nitrogen cycles on Triton, has been modified and applied to Pluto. The model was used to calculate the partitioning of nitrogen between surface frost deposits and the atmosphere, as a function of time for various sets of input parameters. Volatile transport was confirmed to have a significant effect on Pluto's climate as nitrogen moved around on a seasonal time scale between hemispheres, and sublimed into and condensed out of the atmosphere. Pluto's high obliquity was found to have a significant effect on the distribution of frost on its surface. Conditions that would lead to permanent polar caps on Triton were found to lead to permanent zonal frost bands on Pluto. In some instances, frost sublimed from the middle of a seasonal cap outward, resulting in a "polar bald spot". Frost which was darker than the substrate did not satisfy observables on Pluto, in contrast to our findings for Triton. Bright frost (brighter than the substrate) came closer to matching observables. Atmospheric pressure varied seasonally. The amplitudes, and to a lesser extent the phase, of the variation depended significantly on frost and substrate properties. Atmospheric pressure was found to be determined both by Pluto's distance from the sun and by the subsolar latitude. In most cases two peaks in atmospheric pressure were observed annually: a greater one associated with the sublimation of the north polar cap just as Pluto receded from perihelion, and a lesser one associated with the sublimation of the south polar cap as Pluto approached perihelion. Our model predicted frost-free dark substrate surface temperatures in the 50 to 60 K range, while frost temperatures typically ranged between 30 to 40 K. Temporal changes in frost coverage illustrated by our results, and changes in the viewing geometry of Pluto from the Earth, may be important for interpretation of ground-based measurements of Pluto's thermal emission.

Hansen, Candice J.↗

Nitrogen on Mars: Insights from Curiosity

Recent detection of nitrate on Mars indicates that nitrogen fixation processes occurred in early martian history. Data collected by the Sample Analysis at Mars (SAM) instrument on the Curiosity Rover can be integrated with Mars analog work in order to better understand the fixation and mobility of nitrogen on Mars, and thus its availability to putative biology. In particular, the relationship between nitrate and other soluble salts may help reveal the timing of nitrogen fixation and post-depositional behavior of nitrate on Mars. In addition, in situ measurements of nitrogen abundance and isotopic composition may be used to model atmospheric conditions on early Mars.

Stern, J. C.↗

A Pluto thermal model

The recent discovery of nitrogen on Pluto suggests that Pluto's volatile cycles may be similar to those on Neptune's moon Triton. Here, we report the first results of our efforts to apply a thermal model that we developed to study the seasonal nitrogen cycle on Triton to the case of Pluto. The model predicts volatile behavior as a function of time to calculate frost deposit depth, polar cap boundaries, temperature of the frost and substrate, and atmospheric pressure, assuming nitrogen frost deposits in solid-vapor equilibrium with nitrogen in the atmosphere.

Hansen, C. J.↗

Florida Thunderstorms: A Faucet of Reactive Nitrogen to the Upper Troposphere

During the NASA Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) enhanced mixing ratios of nitric oxide were measured in the anvils of thunderstorms and in clear air downwind of storm systems on flights of a Wl3-57F high-altitude aircraft. Mixing ratios greater than l0 - 20 times background were readily observed over distances of 25-120 km due to lightning activity. In many of the Florida storms deposition of NO occurred up to near the tropopause but major deposition usually occurred 1 - 2 km below the tropopause, or mostly within the visible anvil volume formed prior to storm decay. Observations from two storms of very different anvil size and electrical activity allowed estimates of the total mass of NO, vented to the middle and upper troposphere. Using the cloud-to ground (CG) flash accumulations from the National Lightning Detection Network, climatological intra-cloud (IC) to CG ratios, and assuming that CG and IC flashes were of equivalent efficiency for NO production, the ranges of production per flash for a moderate-sized and a large storm were (0.51 - 1.0) x l0(exp 26) and (2.3 - 3.1) x 10(exp 26) molecules NO/flash, respectively. Using the recently determined average global flash rate of 44 8, a gross extrapolation of these two storms to represent possible global annual production rates yield 1.6 - 3.2 and 7.3 - 9.9 Tg(N)/yr, respectively. If the more usual assumption is made that IC efficiency is l/l0th that of CG activity, the ranges of production for the moderate-sized and large storm were (1.3 - 2.7) x l0(exp 26) and (6.0 - 8.1) x l0(exp 26) molecules NO/CG flash, respectively. The estimates from the large storm may be high because there is indirect evidence that the IC/CG ratio was larger than would be derived from climatology. These two storms and others studied did not have flash rates that scaled as approx. H(sup 5) where H is the cloud top altitude. The observed CG flash accumulations and NO(x) mass production estimate for the month of July over the Florida area were compared with a representative 3D global Chemistry-Transport Model (CTMJ that uses the Price et al. lightning parameterization. For two land grid points representing the Florida peninsula the model compared well with the observations: CG flash rates were low by only a factor of approx. 2. When the model grid points included the coastal regions of Florida the flash accumulations were lower than observed by a factor of 3.4 - 4.6. It is recommended that models using the Price et al. parameterization allow any global coastal grid point to maintain the land rather than the marine flash rate parameterization. The convection in this CTM underestimated the actual cloud top heights over Florida by 1 - 2 km and thus the total lightning flash rates and the altitude range of reactive nitrogen deposition. Broad scale (20 - 120 km) median mixing ratios of NO within anvils over Florida were significantly larger than in storms previously investigated over Colorado and New Mexico.

Ridley, B.↗

Air resonance enhanced multiphoton ionization tagging velocimetry

Air resonance enhanced multiphoton ionization (REMPI) tagging velocimetry (ART) was demonstrated in quiescent and supersonic flows. The ART velocimetry method utilizes a wavelength tunable laser beam to resonantly ionize molecular oxygen in air and generate additional avalanche-type ionization of molecular nitrogen. The fluorescence emissions from the first negative and first positive bands of molecular nitrogen are, thus, produced and used for flow tagging. Detailed characterization of ART was conducted, including the effects of oxygen resonance to fluoresce nitrogen, nitrogen fluorescence spectrum, laser energy deposition into quiescent flow showing minimal perturbations in flow, fluorescence lifetime study at various pressures, and line tagging without breakdown. Pointwise velocity measurements within a supersonic flow from a nominal Mach 1.5 nozzle have been conducted and characterized.

Clark, Aleksander↗

Ammonia in northeast Colorado is increasing, rising most quickly in regions close to confined animal feeding operations

The Colorado Front Range urban corridor and nearby agricultural operations are important source regions of atmospheric ammonia (NH 3 ). Upslope flows periodically transport these emissions into Rocky Mountain National Park (RMNP), located 50 km west of the urban corridor, where wet and dry deposition of excess reactive nitrogen (N) impacts ecosystems. Here, we use a combination of in situ passive NH 3 measurements and NH 3 vertical column density retrievals from the Infrared Atmospheric Sounding Interferometer (IASI) to assess variability and changes in NH 3 across three land use categories in the northeast Colorado source region (agricultural, urban, and remote) during the period 2013-2023. A strong seasonal cycle is present across the region with increased NH 3 during summer months. Elevated NH 3 is spatially correlated with the number of permitted animal units in confined animal feeding operations (CAFOs) within 12 km. Ground-level NH 3 concentrations are strongly positively correlated with monthly gridded IASI satellite column densities. Satellite retrievals reveal an increasing trend in NH 3 column amounts of ∼3% per year in agricultural and ∼2% per year in urban sub-regions. The magnitude of the trend observed in NH 3 columns averaged over the agricultural sub-region is > 3 times larger than observed near and over Denver. The largest increases in NH 3 are closely aligned with the distribution of CAFOs. Reductions in particle sulfate associated with declining sulfur dioxide (SO 2 ) emissions could account for only ∼0.1% per year increase in gaseous NH 3 . Wildfire smoke across the region has increased but appears unlikely to explain the majority of the observed NH 3 increase.

54 ENVIRONMENTAL SCIENCES↗

Demonstration of the Feasibility of High Temperature Bearing Lubrication From Carbonaceous Gases

Research has been conducted on silicon nitride pin-on-disk sliding contacts at temperatures of up to 520 C, and four-ball rolling contacts with silicon nitride balls and 52100 steel or silicon nitride races at 590 C. These tests were conducted in a variety of gaseous environments in order to determine the effects of simulated engine exhaust gas on the carbonaceous gas decomposition lubrication scheme. In rolling tests with steel races and exhaust gas the wear track depth was roughly half that of tests run in nitrogen gas alone. The deposition of lubricous microcrystalline graphitic carbon on the rolling surfaces, generated from the carbon monoxide within the exhaust gas mixture, was verified by microfocused Raman spectroscopy. Ten-fold reductions in rolling wear could be achieved by the exhaust gas atmosphere in cases where water vapor was removed or not present. The exhaust gas mixture alone was not found to provide any lubricating effect on silicon nitride sliding contacts, where the rate of wear greatly exceeds the rate of carbon deposition. Directed admixture of acetylene (as low as 5% of the exhaust gas flow rates), has provided reductions in both wear volume and coefficient of friction by factors of 60X and 20X respectively for sliding contacts during the initial 80 m of sliding distance. Exhaust gas atmosphere with the acetylene admixture provided 65OX reductions in steady state wear rate compared to that measured for sliding contacts in dry N2. Such acetylene admixture also augments the ability of the exhaust gas atmosphere to lubricate high-temperature rolling contacts, with up to 25-fold reductions in wear track depth compared to those measured in the presence of N2 alone. In addition to providing some lubricating benefit itself, an important potential role of the exhaust gas from rich mixtures would be to shield bearings from 02. Such shielding enables surface deposition of lubricous pyrolytic carbon from the acetylene admixture, instead of combustion, rendering feasible the continuously replenished solid lubrication of high-temperature bearing surfaces.

Blanchet, Thierry A.↗

Coupling of Volatile Transport and Internal Heatflow on Triton

Recently Brown et al. (Science 250, 1991) showed that Trition's internal heat source could amount to 5-20% of the absorbed insolation on Trition, thus significantly affecting volatile transport and stmospheric pressure.

Trition heatflow nitrogen ice deposits↗

Seasonal Nitrogen Cycles on Pluto

A thermal model, developed to predict seasonal nitrogen cycles on Triton, has been modified and applied to Pluto. The model is used to calculate the partitioning of nitrogen between surface frost deposits and the atmosphere, as a function of time for various sets of input parameters.

thermal models↗