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At least 127 records · Page 7

On the Interaction of CO and NH3 with BH3 and BF3

BH3CO, BF3CO, BH3NH3, and BF3NH3 have been studied using density functional theory (DFT). The computed geometries are in reasonable agreement with experiment. BF3CO is found to be weakly bound. The binding energies of BH3CO, BH3NH3 , and BF3NH3 have also been computed using the coupled cluster singles and doubles level of theory, including a perturbational estimate of the connected triples [CCSD(T)]. These CCSD(T) calculations are performed using correlation consistent polarized-valence triple-zeta basis sets. These are expected to be the most accurate binding energies to date. The DFT binding energies are in good agreement with those obtained at the CCSD(T) level. The bonding is analyzed using the constrained space orbital variation (CSOV) technique. In addition to analyzing the bonding in BH3CO, BH3NH3, and BF3NH3, the CSOV approach is used to study why the bonding in BF3CO is so weak.

Bauschlicher, Charles W., Jr.↗

Measurement Report :Emission Factors of NH3 and NHx for Wildfires and Agricultural Fires in the United States

During the 2019 Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) study, the NASA DC-8 carried out in situ chemical measurements in smoke plumes emitted from wildfires and agricultural fires in the contiguous United States. The DC-8 payload included a modified proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) for the fast measurement of gaseous ammonia (NH 3 ) and a high-resolution time-of-flight aerosol mass spectrometer (AMS) for the fast measurement of submicron particulate ammonium (NH 4 + ). We herein report data collected in smoke plumes emitted from 6 wildfires in the Western United States, 2 prescribed grassland fires in the Central United States, 1 prescribed forest fire in the Southern United States, and 66 small agricultural fires in the Southeastern United States. Smoke plumes contained double to triple digit ppb levels of NH 3 . In the wildfire plumes, a significant fraction of NH 3 had already been converted to NH 4 + at the time of sampling (≥2 h after emission). Substantial amounts of NH 4 + were also detected in freshly emitted smoke from corn and rice field fires. We herein present a comprehensive set of emission factors of NH 3 and NH x , with NH x = NH 3 + NH 4 + . Average NH 3 and NH x emission factors for wildfires in the Western United States were 1.86±0.75 g kg −1 and 2.47±0.80 g kg −1 of fuel burned, respectively. Average NH 3 and NH x emission factors for agricultural fires in the Southeastern United States were 0.89±0.58 and 1.74±0.92 g kg −1 , respectively. Our data show no clear inverse correlation between modified combustion efficiency (MCE) and NH 3 emissions. The observed NH 3 emissions were significantly higher than measured in previous laboratory experiments in the FIREX FireLab 2016 study.

Laura Tomsche↗

Ammonia and Methane Dairy Emission Plumes in the San Joaquin Valley of California from Individual Feedlot to Regional Scales

Agricultural ammonia (NH3) emissions are highly uncertain, with high spatiotemporal variability and a lack of widespread in situ measurements. Regional NH3 emission estimates using mass balance or emission ratio approaches are uncertain due to variable NH3 sources and sinks as well as unknown plume correlations with other dairy source tracers. We characterize the spatial distributions of NH3 and methane (CH4) dairy plumes using in situ surface and airborne measurements in the Tulare dairy feedlot region of the San Joaquin Valley, California, during the NASA Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality 2013 field campaign. Surface NH3 and CH4 mixing ratios exhibit large variability with maxima localized downwind of individual dairy feedlots. The geometric mean NH3:CH4 enhancement ratio derived from surface measurements is 0.15 +/- 0.03 ppmv ppmv−1. Individual dairy feedlots with spatially distinct NH3 and CH4 source pathways led to statistically significant correlations between NH3 and CH4 in 68% of the 69 downwind plumes sampled. At longer sampling distances, the NH3:CH4 enhancement ratio decreases 20-30%, suggesting the potential for NH3 deposition as a loss term for plumes within a few kilometers downwind of feedlots. Aircraft boundary layer transect measurements directly above surface mobile measurements in the dairy region show comparable gradients and geometric mean enhancement ratios within measurement uncertainties, even when including NH3 partitioning to submicron particles. Individual NH3 and CH4 plumes sampled at close proximity where losses are minimal are not necessarily correlated due to lack of mixing and distinct source pathways. Our analyses have important implications for constraining NH3 sink and plume variability influences on regional NH3 emission estimates and for improving NH3 emission inventory spatial allocations.

Miller, David J.↗

A carbon dioxide/methane greenhouse atmosphere on early Mars

One explanation for the formation of fluvial surface features on early Mars is that the global average surface temperature was maintained at or above the freezing point of water by the greenhouse warming of a dense CO2 atmosphere; however, Kasting has shown that CO2 alone is insufficient because the formation of CO2 clouds reduces the magnitude of the greenhouse effect. It is possible that other gases, such as NH3 and CH4, were present in the early atmosphere of Mars and contributed to the greenhouse effect. Kasting et al. investigated the effect of NH3 in a CO2 atmosphere and calculated that an NH3 mixing ratio of approximately 5 x 10 (exp -4) by volume, combined with a CO2 partial pressure of 4-5 bar, could generate a global average surface temperature of 273 K near 3.8 b.y. ago when the fluvial features are believed to have formed. Atmospheric NH3 is photochemically converted to N2 by ultraviolet radiation at wavelengths shortward of 230 nm; maintenance of sufficient NH3 concentrations would therefore require a source of NH3 to balance the photolytic destruction. We have used a one-dimensional photochemical model to estimate the magnitude of the NH3 source required to maintain a given NH3 concentration in a dense CO2 atmosphere. We calculate that an NH3 mixing ratio of 10(exp -4) requires a flux of NH3 on the order of 10(exp 12) molecules /cm-s. This figure is several orders of magnitude greater than estimates of the NH3 flux on early Mars; thus it appears that NH3 with CO2 is not enough to keep early Mars warm.

Brown, L. L.↗

Very Large Array Ammonia Observations of the HH 111/HH 121 Protostellar System: A Detection of a New Source with a Peculiar Chemistry

We present the results of Very Large Array NH3 (J, K) = (1, 1) and (2, 2) observations of the HH 111/HH 121 protostellar system. HH 111, with a spectacular collimated optical jet, is one of the most well-known Herbig-Haro objects. We report the detection of a new source, NH3-S, in the vicinity of HH 111/HH 121 (approximately 0.03 parsecs from the HH 111 jet source) in two epochs of the ammonia observations. This constitutes the first detection of this source, in a region that has been thoroughly covered previously by both continuum and spectral line interferometric observations. We study the kinematic and physical properties of HH 111 and the newly discovered NH3-S. We also use HCO plus and HCN (J=4-3) data obtained with the James Clerk Maxwell Telescope and archival Atacama Large Millimeter/submillimeter Array (sup 13) CO, (sup 12) CO, and C (sup 18) O (J=2-1), N2D plus (J=3-2), and (sup 13) CS (J=5-4) data to gain insight into the nature of NH3-S. The chemical structure of NH3-S shows evidence for "selective freeze-out," an inherent characteristic of dense cold cores. The inner part of NH3-S shows subsonic nonthermal velocity dispersions indicating a "coherent core," while they increase in the direction of the jets. Archival near- to far-infrared data show no indication of any embedded source in NH3-S. The properties of NH3-S and its location in the infrared dark cloud suggest that it is a starless core located in a turbulent medium, with the turbulence induced by Herbig-Haro jets and associated outflows. More data are needed to fully understand the physical and chemical properties of NH3-S and if/how its evolution is affected by nearby jets.

James Clerk Maxwell Telescop↗

Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

Huang, Cunping↗

Hot hydrogen atom reactions moderated by H2 and He

Photolysis experiments were performed on the H2-CD4-NH3 and He-CD4-NH3 systems. The photolysis (1849 A) involved only NH3. Mixtures of H2:CD4:NH3 included all combinations of the ratios (200,400,800):(10,20,40):4. Two He:CD4:NH3 mixtures were examined where the ratios equalled the combinations 100:(10,20):4. Abstraction of a D from CD4 by the photolytically produced hot hydrogen from ammonia was monitored by mass spectrometric determination of HD. Both experiment and semiempirical hot-atom theory show that H2 is a very poor thermalizer of hot hydrogens with excess kinetic energy of about 2 eV. Applications of the hard-sphere collision model to the H2-CD4-NH3 system resulted in predicted ratios of net HD production to NH3 decomposition that were two orders of magnitude smaller than the experimental ratios. On the other hand, helium is found to be a very efficient thermalizer; here, the classical model yields reasonable agreement with experiments. Application of a semiempirical hot-atom program gave quantitative agreement with experiment for either system.

Aronowitz, S.↗

Ammonia Offgassing from SA9T

NH3 is a degradation product of SA9T, a solid-amine sorbent developed by Hamilton Sundstrand, that is continually emitted into the gas stream being conditioned by this sorbent. NH3 offgassing rates were measured using FTIR spectroscopy using a packed bed at similar contact times as offgassing tests conducted at Hamilton Sundstrand and at the Ames Research Center. The bed was challenged with moist air at several flow rates and humidities and NH3 concentration of the effluent was measured for several hours. The NH3 offgassing rates in open-loop testing were calculated from the steady state outlet NH3 concentration and flow rate. NH3 offgassing rates from SA9T were found to be influenced by the contact time with the adsorbent (flow rate) and by the humidity of the inlet gas stream, which are consistent with previous studies. Closed-loop vacuum-swing adsorption cycling rates verified that NH3 offgassing continues when a constant source of water vapor is present.

Monje, Oscar↗

Quantifying Spatial and Seasonal Variability in Atmospheric Ammonia with In Situ and Space-Based Observations

Ammonia plays an important role in many biogeochemical processes, yet atmospheric mixing ratios are not well known. Recently, methods have been developed for retrieving NH3 from space-based observations, but they have not been compared to in situ measurements. We have conducted a field campaign combining co-located surface measurements and satellite special observations from the Tropospheric Emission Spectrometer (TES). Our study includes 25 surface monitoring sites spanning 350 km across eastern North Carolina, a region with large seasonal and spatial variability in NH3. From the TES spectra, we retrieve a NH3 representative volume mixing ratio (RVMR), and we restrict our analysis to times when the region of the atmosphere observed by TES is representative of the surface measurement. We find that the TES NH3 RVMR qualitatively captures the seasonal and spatial variability found in eastern North Carolina. Both surface measurements and TES NH3 show a strong correspondence with the number of livestock facilities within 10 km of the observation. Furthermore, we find that TES H3 RVMR captures the month-to-month variability present in the surface observations. The high correspondence with in situ measurements and vast spatial coverage make TES NH3 RVMR a valuable tool for understanding regional and global NH3 fluxes.

Pinder, Robert W.↗

Photosynthesis of organic compounds in the atmosphere of Jupiter

An efficient conversion of CH4 to hydrocarbons and HCN takes place when NH3 is photolysed in the presence of CH4, H2, and He using a 184.9 nm light source. The extent of NH3 decomposition after a 1 hr exposure was determined spectrophotometrically; CH4, N2, and C2 and C3 hydrocarbons were detected and analyzed by mass spectrometry. Photolysis of one molar equivalent of NH3 results in the loss of 0.84 molar equivalent of CH4, which apparently reacts with hot hydrogen atoms produced by photolysis. The 8% of the NH3 which is not converted to N2 probably is converted to organic amines and nitrile derivatives. The results indicate that NH3 photolysis is a highly probable mechanism for the conversion of methane to more complex hydrocarbons in the upper atmosphere of Jupiter, and predict the occurrence of HCN, NH2NH2, and higher hydrocarbons in the Jovian atmosphere above the NH3 clouds.

Ferris, J. P.↗

Reaction of NH2 with NO and O2

Experiments were performed on the photooxidation of NH3 at room temperature and the photolysis of NH3-NO mixtures in order to determine the reaction paths of NH2 with O2. NH3 was photolyzed (NH3 + E yields NH2 + H) in the presence of O2 above 0.6 torr at 213.9 nm and 25 C, producing N2 and N2O. Only N2 and N2O were produced with any significant quantum yield, and their quantum yield was invariant with reaction conditions, which imposes a great number of constraints reducing the number of possible reactions greatly. It is argued that the N2 must be produced from the NH2O2 radical which was produced by the reaction between NH2 and O2. Subsequent reactions leading to N2 and N2O are speculative. In the photolysis of NH3 in the presence of NO and NO-O2 mixtures, the products identified were N2, H2, and N2O. Without the presence of O2, the reaction scheme after photolysis is (2) NH2 + NO yields N2 + H2O, (3) H + NO + M yields HNO + M, (4) H + HNO yields H2 + NO, and (5) 2HNO yields N2O + H2O. The average value for the ratio k3 times the square root of k5 divided by k4 was computed to be (1.6 plus or minus 0.6) times 10 to the minus 28th cm to the exponent 9/2 per square root sec. In addition, the presence of 113 mtorr of O2 had no effect on the quantum yields of N2 or H2, so it appears that it does not deactivate electronically excited NH3.

Jayanty, R. K. M.↗

The infrared spectrum of ammonia hydrate - Explanation for a reported ammonia phase

A number of anomalous spectra of solid NH3 deposited from the vapor phase have appeared in the literature. These spectra have been ascribed to a new phase of NH3. In the experiment reported here these anomalous spectra were reproduced by depositing a thin film from a mixture of gaseous NH3 and H2O and annealing this film at a temperature of 162 K. The thin film spectra showed excellent agreement with recent data on NH3.H2O. The anomalous 'NH3' spectra are, therefore, seen to be caused by H2O contamination of solid NH3 with formation of NH3 hydrate.

Still, G.↗

State-to-state rotational energy-transfer measurements in the nu(2) = 1 state of ammonia by infrared-infrared double resonance

The state-resolved rotational (R-R, R-T) energy transfer in (N-14)H3 (for NH3-NH3 and NH3-Ar collisions) was studied using an IR double-resonance laser spectroscopic technique. Measurements of both the total rate of depopulation by collisions, and the rates of transfer into specific final rovibrational states (v,J,K) were performed using time-resolved tunable diode laser absorption spectroscopy. A kinetic master-equation analysis of time-resolved level populatons was carried out, yielding state-to-state rate constants and propensity rules for NH3-NH3 and NH3-Ar collisions.

Abel, Bernd↗

The Spatial Variation of Water and Ammonia near Jupiter's Great Red Spot

The CSHELL spectrometer at NASA's Infrared Telescope Facility was used in August 1996 to observe Jupiter at 5.18 microns. This wavelength sounds the 3-8 bar region in Jupiter's deep troposphere. A 1-arcsec-wide slit was aligned east-west on Jupiter and stepped from north to south across the Great Red Spot (GRS). Within our spectral bandpass are absorption lines of NH3 and a hot band of CH4. Radiative transfer models indicate that the strength of the CH4 feature is anti-correlated with gaseous H2O between 3 and 6 bars. The CH4 feature is predicted to be very strong for H2O abundances less than 10ppm and it should vanish when H2O > 300ppm. The depths of the observed CH4 and NH3 absorption features varied dramatically near the GRS. The center and east side (planetocentric) of the GRS is dry in both volatiles as indicated by strong CH4 absorption and a weak NH3 line. The CH4 line vanishes and the NH3 feature grows stronger on the west side of the GRS. We interpret this as due to a real variation in both volatiles - H2O and NH3 - due to a common dynamical mechanism. Water clouds are expected to be accompanied by saturated gaseous H2O profiles between 3 and 5 bars. The Galileo imaging team (Banfield et al 1998 Icarus 135, p230) deduced the presence of a cloud near the 4-bar level northwest of the GRS. Our data indicate that this same region is volatile rich; thus the combination of the two datasets provides a compelling case for a water cloud at this location. The deep volatile abundance does not correlate with 5-micron continuum opacity near the GRS. This suggests that the spatial variation of the 5-micron flux near the GRS is due primarily to NH3 clouds, rather than H2O clouds.

Bjoraker, G. L.↗

Evolutionary status of the pre-protostellar core L1498

L1498 is a classic example of a dense cold pre-protostellar core. To study the evolutionary status, the structure, dynamics, and chemical properties of this core we have obtained high spatial and high spectral resolution observations of molecules tracing densities of 10(3)-10(5) cm-3. We observed CCS, NH3, C3H2, and HC7N with NASA's DSN 70 m antennas. We also present large-scale maps of C18O and 13CO observed with the AT&T 7 m antenna. For the high spatial resolution maps of selected regions within the core we used the VLA for CCS at 22 GHz, and the Owens Valley Radio Observatory (OVRO) MMA for CCS at 94 GHz and CS (2-1). The 22 GHz CCS emission marks a high-density [n(H2) > 10(4) cm -3] core, which is elongated with a major axis along the SE-NW direction. NH3 and C3H2 emissions are located inside the boundary of the CCS emission. C18O emission traces a lower density gas extending beyond the CCS boundary. Along the major axis of the dense core, CCS, NH3 and C3H2 emission show evidence of limb brightening. The observations are consistent with a chemically differentiated onion-shell structure for the L1498 core, with NH3 in the inner and CCS in the outer parts of the core. The high angular resolution (9"-12") spectral line maps obtained by combining NASA Goldstone 70 m and VLA data resolve the CCS 22 GHz emission in the southeast and northwest boundaries into arclike enhancements, supporting the picture that CCS emission originates in a shell outside the NH3 emitting region. Interferometric maps of CCS at 94 GHz and CS at 98 GHz show that their emitting regions contain several small-scale dense condensations. We suggest that the differences between the CCS, CS, C3H2, and NH3 emission are caused by a time-dependent effect as the core evolves slowly. We interpret the chemical and physical properties of L1498 in terms of a quasi-static (or slowly contracting) dense core in which the outer envelope is still growing. The growth rate of the core is determined by the density increase in the CCS shell resulting from the accretion of the outer low-density gas traced by C18O. We conclude that L1498 could become unstable to rapid collapse to form a protostar in less than 5 x 10(6) yr.

NASA Discipline Exobiology↗

In Situ Measurements of Ammonia In Plumes Emitted From Wildfires And Agricultural Fires in the US

Emissions of trace gases and particles from fires have a major impact on climate, visibility, air quality, and public health. Biomass burning emissions include reactive nitrogen gases, among which ammonia (NH3) plays a prominent role. NH3 is a short-lived gas that acts as precursor for secondary inorganic aerosols. This process is still poorly constrained in downwind fire plumes. In summer 2019, NASA and NOAA carried out the joint airborne FIREX-AQ (Fire Influence on Regional to global Environments and Air Quality) mission over the continental US to sample plumes from wildfires and agricultural fires. On board the NASA DC-8, we used a modified PTR-ToF-MS instrument for measuring NH3 in situ and at high time resolution. Over the course of the mission, we collected a large set of NH3 data in plumes emitted from fires differing in fuel type and burning stage. Herein, we will present the measured NH3 emissions ratios and factors, compare them with the literature, and investigate the dependence of NH3 emissions on fuel type and burning conditions.

ammonia↗