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Nucleobases and Prebiotic Molecules in Organic Residues Produced from the Ultraviolet Photo-Irradiation of Pyrimidine in NH3 and H2O+NH3 Ices

Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases the information subunits of DNA and RNA are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab-initio calculations have already shown that the irradiation of pyrimidine in pure H2O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH3:pyrimidine and H2O:NH3:pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

Nuevo, Michel↗

Application of shock wave data to earth and planetary science

It is pointed out that shock wave data for: (1) low temperature condensable gases H2 and He, (2) H2O, CH4, NH3, CO, CO2, and N2 ices, and (3) silicates, metals, oxides and sulfides have many applications in geophysics and planetary science. The present paper is concerned with such applications. The composition of planetary interiors is discussed, taking into account the division of the major constituent of the planets in three groups on the basis of 'cosmic abundance' arguments, the H-He mixtures in the case of Jupiter and Saturn, shock wave data for hydrogen, and constraints on the internal structure of Uranus and Neptune. Attention is also given to the earth's mantle, shock wave data for mantle materials, the earth's core, impacts on planetary surfaces, elastic wave velocities as a function of pressure along the Hugoniot of iron, and reactions which yield the CO2 bearing atmospheres for Venus, earth, and Mars.

Ahrens, T. J.↗

Evaluating the Adsorptive Capabilites of Chemsorb 1000 and Chemsorb 1425

The removal of trace contaminants from spacecraft cabin air is necessary for crew health and comfort during long duration space exploration missions. The air revitalization technologies used in these future exploration missions will evolve from current ISS ISS State-of-Art (SOA) and is being designed and tested by the Advanced Exploration Systems (AES) Program's Atmosphere Resource Recovery and Environmental Monitoring (ARREM) project. The ARREM project is working to mature optimum atmosphere revitalization and environmental monitoring system architectures to enable exploration beyond Lower Earth Orbit (LEO). The Air Revitalization Lab at KSC is one of six NASA field centers participating in the ARREM that specializes in adsorbent and catalyst characterization with simulated spacecraft gas streams using combinations of pressure, O2 partial pressure, CO2 partial pressure, and humidity that are representative of a range of anticipated cabin atmospheric conditions and loads. On board ISS, the Trace Contaminant Control Subassembly (TCCS) provides active control of trace contaminants from the cabin atmosphere utilizing physical adsorption, thermal catalytic oxidation, and chemical adsorption processes. High molecular weight contaminants and ammonia (NH3) are removed a granular activated carbon treated with approx. 10% by weight phosphoric acid (H3PO4) (B-S Type 3032 4×6 mesh), which is expendable and is periodically refurbished. The Type 3032 granular activated carbon bed is no longer commercially available and therefore it is important to characterize the efficiency and capacity of commercially available NH3 sorbents. This paper describes the characterization of two Molecular Products LTD activated carbons: Chemsorb 1000 and Chemsorb 1425. Untreated activated carbons (e.g. Chemsorb 1000) remove contaminants by physisorption, which concentrates the contaminant within the pores of the carbon while letting air to pass through the sorbent4. Low molecular weight or polar gases (e.g. HCl, SO2, formaldehyde, and NH3) are not removed by physisorption and typically require chemisorption for removal. Treated activated carbons (e.g. Chemsorb 1425) are impregnated with a a chemical agent (e.g. phosphoric acid) that reacts with those gases, converting them to solids or salts within the carbon and removes them from the air stream. This process occurs via neutralization or catalysis reactions and adsorption capacity is exhaustedwhen the available impregnated chemicals are consumed. Moisture affects removal performance since adsorption sites within the pores are filled with water. The performance of impregnated carbons may be enhanced by moisture content because the mechanisms of contaminant removal are chemical reactions that occur in reagents contained within the pores. The adsorptive capacity data (mol/kg) of Chemsorb 1000 and 1425 for gas mixtures (ethanol, acetone, toluene, acetaldehyde, dichloromethane, and xylene) was measured with 40% relative humidity at 23 deg C air temperature. The adsorptive capacity data (mol/kg) of Chemsorb 1425 was measured using NH3 gas streams.

adsorptive capacities↗

An investigation of sulfate production in clouds using a flow-through chemical reactor model approach

A flow-through chemical reactor model is developed to describe the mass transfer and chemical processes that atmospheric gases undergo in clouds. The model includes the simultaneous absorption of SO2, NH3, O3, NO(x), HNO3, CO2 and H2O2, the accompanying dissociation and oxidation reactions in cloud water, considers electrical neutrality, and includes qualitative parameterization of cloud microphysics. The model is used to assess the importance of the oxidation reactions H2O2-S(IV), O3-S(IV), and S(IV)-Mn(2+) catalysis, and the effects of cloud parameters such as drop size, rain intensity, liquid water content, and updraft velocity. Both precipitating and nonprecipitating clouds are studied. Model results predict sulfate production rates varying from 3 percent/hr to 230 percent/hr. The actual rate is highly dependent on the chemical composition of the uptake air and the physical conditions of the cloud. Model results also show that both the H2O2 and the O3 oxidation reactions can be significant.

Hong, M. S.↗

Earth's Early Reduced Atmospheres

Earth’s early atmosphere evolved in response to cosmic impacts, photochemistry generated by the copious extreme ultraviolet radiation emitted by the young Sun, hydrogen escape, mineral redox buffering, the evolution of iron in the mantle, and the character of crustal weathering and subduction. No single chemical composition, surface pressure, or temperature was typical. After the biggest impacts the temperature likely rose above 3000 K and the atmosphere held rock vapor. As the atmosphere cooled its constituents rained out: first the silicates, then the geochemical volatiles (such as salt), and last the water. Depending on the size of the impact, cooling took thousands to millions of years. Between impacts the atmosphere was thick with gases like CO2, H2, and CH4 that do not condense at Earth but provide greenhouse warming that could easily have maintained surface temperatures in excess of 500 K. At some point the early atmosphere must have been conducive to the evolution of organic chemistry and the origin of life. It was therefore --- at times --- dominated by reduced gases like hydrogen and methane. Hydrogen-methane atmospheres are easily formed thermochemically after major impacts if H2O and CO2 were present on Earth in quantities consistent with their inventories on Earth today – the key is high pressure. Hydrogen-methane atmospheres slowly break down over millions of years by hydrogen escape and photochemistry. At first methane decomposes into tars and nitriles that precipitate, but later as the atmosphere grows more oxidized from hydrogen escape the methane oxidizes to CO and CO2, with a small fraction going to HCN. Impacts can also produce NH3 directly from N2 and H2O, which is expected to rain out with the H2O. As impacts grew infrequent the climate cooled in response to the fixing of CO2 as carbonate and carbonate subduction. Eventually the CO2 was mostly removed to the mantle and the surface mostly frozen.

Zahnle, Kevin↗

Carbon Nanotube Gas Sensor Using Neural Networks

The need to identify the presence and quantify the concentrations of gases and vapors is ubiquitous in NASA missions and societal applications. Sensors for air quality monitoring in crew cabins and ISS have been actively under development (Ref. 1). In particular, measuring the concentration of CO2 and NH3 is important because high concentrations of these gases pose a risk to ISS crew health. Detection of fuel and oxidant leaks in crew vehicles is critical for ensuring mission safety. Accurate gas and vapor concentrations can be measured, but this typically requires bulky and expensive instrumentation. Recently, inexpensive sensors with low power demands have been fabricated for use on the International Space Station (ISS). Carbon Nanotube (CNT) based chemical sensors are one type of these sensors. CNT sensors meet the requirements for low cost and ease of fabrication for deployment on the ISS. However, converting the measured signal from the sensors to human readable indicators of atmospheric air quality and safety is challenging. This is because it is difficult to develop an analytical model that maps the CNT sensor output signal to gas concentration. Training a neural network on CNT sensor data to predict gas concentration is more effective than developing an analytic approach to calculate the concentration from the same data set. With this in mind a neural network was created to tackle this challenge of converting the measured signal into CO2 and NH3 concentration values.

Norman, Thaddeus J.↗

Chemical waste disposal in space by plasma discharge

An inductively coupled plasma discharge apparatus operating at 13.56 MHz and with electrical power up to 2.5 kW was constructed. The efficiency of this device to destroy various gases expected to be carried aboard the Space Station was tested. By expressing the efficiency of the device in terms of G-value (the number of molecules decomposed per 100 eV of energy absorbed), the results are compared with known efficiencies of ionizing radiation to destroy these same gases. In the case of ammonia, it was found that in the inductively coupled device, the destruction efficiency, G(-NH3) varied from 6.0 to 32.0 molecules/100 eV, depending on conditions. It was also found that capacitatively coupled discharges were less efficient in destroying NH2 than the inductively coupled discharge. In the case NH2 destruction, it was found that the G(-NH3) was a qualitative guide to the efficiencies of plasmas. The plasma device was also used to destroy nitrous oxide and methane. It is shown how the G-value for the destruction of any gas can be computed theoretically from a knowledge of the electron velocity distribution, the various electron molecule scattering cross sections, and the rate constants for the reactions of secondary species.

Baird, James K.↗

Elemental, isotopic and molecular abundances in comets

The chemical composition of comet nuclei and the factors affecting it are discussed, summarizing the results of recent theoretical, experimental, and observational investigations. Consideration is given to the evidence supporting the view that the nucleus is radially differentiation (except for a thin outer layer), surface differentiation by heat processing and outgassing, and mantle buildup on an undifferentiated core. The nature of the refractory and volatile components is examined, and the elemental and isotopic compositions are given in tables and characterized. The uncertain (except for H2O) molecular composition of the volatile fraction is considered, and it is suggested that some oxides or aldehydes (such as CO, CO2, and H2CO), but no large amounts of fully hydrogenated compounds (such as CH4 and NH3) are included.

Delsemme, A. H.↗

Descent Without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds

The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NHþ 4 and SO2 making SO2 4 by H+ and e - transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.

Europa↗

Chemistry of a polluted cloudy boundary layer

A one-dimensional photochemical model for cloud-topped boundary layers has been developed to include descriptions of gas- and aqueous-phase chemistry and the radiation field in and below the cloud. The model is applied to the accumulation of pollutants during a wintertime episode with low stratus over Bakersfield, CA. The mechanisms of sulfate production and the balance between the concentrations of acids and bases are examined. It is shown that most of the sulfate production may be explained by the Fe(III)-catalyzed autoxidation of S(IV). Another source of sulfate is the oxidation of SO2 by OH in both the gas and the aqueous phase. It is shown that the sulfate production in the model is controlled by the availability of NH3. It is suggested that this explains the balance observed between total concentration of acids and bases.

Jacob, Daniel J.↗

Application of a Chemiluminescence Detector for the Measurement of Total Oxides of Nitrogen and Ammonia in the Atmosphere

By means of the thermal conversion of nitrogen dioxide to the nitric oxide, the chemiluminescent nitric oxide monitor, based on the nitric oxide plus ozone reaction, may be used for monitoring nitrogen dioxide plus nitric oxide (NO(x)). Under conditions previously described, ammonia is also converted to nitric oxide and therefore interferes. A metal surface, gold wool or stainless steel, operated at two different temperatures has been used to convert only nitrogen dioxide or nitrogen dioxide plus ammonia. Quantitative conversion of nitrogen dioxide to nitric oxide has been obtained at temperatures as low as 200 C. Conversion of ammonia is effected at temperatures of 300 C or higher. By the addition of a converter the basic nitric oxide monitor may be used for measuring NO(x) or NO(x) plus ammonia. As an alternate mode, for a fixed high temperature, a specific scrubber is described for removing NH3 without affecting NO2 concentrations.

Hodgeson, J. A.↗

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗

The fate of the hydroxyl radical in the earth's primitive atmosphere and implications for the production of molecular oxygen

Behavior of the hydroxyl radical produced by the photolysis of water vapor in the earth's early atmosphere is examined. Because of the substantial OH radical reactivity with trace species (CO, HCl, SO2, H2S, NH3, and CH4) the formation of molecular oxygen may be prevented, even at a trace species mixing ratio. The photolysis rate of H2O, with corrections for hydrogen exospheric escape, is capable of describing the oxidation of the atmosphere and crust but may not be used to determine the rate of molecular oxygen generation without consideration of the various OH-trace species reactions.

Vander Wood, T. B.↗

Nitric acid and ammonia emissions from a mid-latitude prescribed wetlands fire

The first simultaneous measurements of gaseous nitric acid and ammonia in the smoke plume of a wetlands biomass burn were obtained. The measurements were made using tungsten oxide-coated diffusion denuder tubes from a helicopter during a prescribed burn on November 9, 1987, at the Merritt Island National Wildlife Refuge, located at the NASA John F. Kennedy Space Center, Florida. The mean NH3 and HNO3 mixing ratios measured in the smoke plume were 19 ppbv and 14 ppbv, respectively, both significantly higher than background mixing ratios. Nitric acid correlated well with carbon dioxide produced by the combustion. The mean CO2-normalized emission ratio for HNO3 was found to be 0.00012. Ammonia, however, dit not correlate well with CO2, suggesting a more complex relationship between combustion and production/release of NH3.

Lebel, P. J.↗

A simulation experiment of photochemical reactions in the mesosphere

An ionospheric simulation experiment has been performed in a large vacuum chamber. The chamber is filled with NO and other gases including N2, O2, CO2, NH3 and H2O in the pressure range of 0.01 torr. A lamp which produces photons at 1236- and 1165-A by means of microwave discharge in krypton is utilized as an ionization source. In addition to 30+ large quantities of the water cluster ions 55+, H3O(+).(H2O)2, 73+, H3O(+).(H2O)3 and 91+, H3O(+).(H2O)4 were observed when nitric oxide and water were present. This closely approximates the condition of the terrestrial D region. After long periods of UV irradiation 74+ and 104+ ions grow in intensity. These ions are tentatively identified as NO(+).N2O and NO(+).NO.N2O. In addition the series 18+, 36+, 54+, and 72+ is detected which can be labeled NH4(+), NH4(+).(H2O), NH4(+).(H2O)2 and NH4(+).(H2O)3. These same species of ions are observed with the introduction of ammonia into the chamber. Presumably both N2O and NH3 are products of the photolysis.

Fugono, N.↗

Seasonal nitrous oxide flux from an intensively managed pasture in a humid subtropical ecosystem

Nitrous oxide (N2O) flux from vented chambers was measured over intensively and minimally managed bermuda grass hay meadows in a humid, subtropical ecosystem for several years during scheduled sampling protocol following harvest, fertilization and rainfall events while measuring diel N2O emissions once during each of 5 seasonal day growth cycles which divided each calendar year. Soil pools of nitrite NO2(-), nitrate NO3(-), and ammonia (NH3) were measured in soil samples taken at 2 and 10 cm depths during each emission collection to determine transformations of the nitrogen pools coupled with N2O emissions. The highest diel N2O emission occur midday in the Spring cycle, measuring 9.0 g N/ha/d only for several weeks, while emissions dropped to less than 1.0 g N/ha/day during hot, dry, and colder months. Intensively managed meadows (4 fertilizations and harvests per year plus pest management) induced higher seasonal N2O emissions than minimal treatment (1 fertilization and harvest) averaging 2.75 and 5.97 g N/ha/day. Nitrous oxide emission data as responses to soil parameters and environmental parameters were also measured where air temperature, soil moisture, and fertilization were the most powerful factors.

Brams, Eugene A.↗

Emissions from Forest Fires near Mexico City

The emissions of NOx (defined as NO (nitric oxide) + NO2 (nitrogen dioxide)) and hydrogen cyanide (HCN), per unit amount of fuel burned, from fires in the pine forests that dominate the mountains surrounding Mexico City (MC) are about 2 times higher than normally observed for forest burning. The ammonia (NH3) emissions are about average for forest burning. The upper limit for the mass ratio of NOX to volatile organic compounds (VOC) for these MC-area mountain fires was approximately 0.38, which is similar to the NOx/VOC ratio in the MC urban area emissions inventory of 0.34, but much larger than the NOx/VOC ratio for tropical forest fires in Brazil (approximately 0.068). The nitrogen enrichment in the fire emissions may be due to deposition of nitrogen-containing pollutants in the outflow from the MC urban area. This effect may occur worldwide wherever biomass burning coexists with large urban areas (e.g. the tropics, southeastern US, Los Angeles Basin). The molar emission ratio of HCN to carbon monoxide (CO) for the mountain fires was 0.012 +/- 0.007, which is 2-9 times higher than widely used literature values for biomass burning. The ambient molar ratio HCN/CO in the MC-area outflow is about 0.003 +/- 0.0003. Thus, if only mountain fires emit significant amounts of HCN, these fires may be contributing about 25% of the CO production in the MCarea (approximately 98-100 W and 19-20 N). Comparing the PM10/CO and PM2.5/CO mass ratios in the MC Metropolitan Area emission inventory (0.01 15 and 0.0037) to the PM1/CO mass ratio for the mountain fires (0.133) then suggests that these fires could produce as much as approximately 79-92% of the primary fine particle mass generated in the MC-area. Considering both the uncertainty in the HCN/CO ratios and secondary aerosol formation in the urban and fire emissions implies that about 50 +/- 30% of the "aged" fine particle mass in the March 2006 MC-area outflow could be from these fires.

Yokelson, R.↗

Cropland and Land-Clearing Emission Factors From Firex-AQ

The Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign is a NOAA/NASA interagency intensive study of North American fires that took place from July to September 2019. Agricultural fires were sampled on 7 flights from August 21st to September 3rd, 2019. We present emission factors for gas-phase and aerosol-phase species for the different fuel types identified during the campaign. We discuss the dependence of these emission factors on both fuel type and burning characteristics such as modified combustion efficiency (MCE). We analyze 73 fires encompassing four different agricultural fuels (corn, rice, soybean, wheat) and four different types of land-clearing fuels (grass, slash, pile, shrub). Approximately half of all sampled fires were burning corn agricultural residue. We report emission factors for 118 VOCs, where two thirds of emissions are made up of species with lifetimes against oxidation by OH of less than 12 hours (near-field impacts) and the remainder have longer-lifetimes (far-field impacts). We also include an additional 9 aerosol species, 12 halogenated species, 5 sulfur-containing species, and 22 nitrogen-containing species, including NH3 and NOx. There is a statistically significant difference in MCE between agricultural and land-clearing fires that accounts for some of the differences in emission factors across these fuels. VOCs generally have a strong negative correlation with MCE but with different slopes across fuel types. There is a significant positive relationship between MCE and three gas-phase (NO, NO2, SO2) and two aerosol-phase (pCl, pNH4) species. Many emission factors show additional dependence factors beyond MCE that could be related to fuel composition, fire temperature, soil moisture, or other possible differences in burning conditions. Therefore, important differences in emission factors may result when averaging together different types of agricultural and land-clearing fuels in compilations for use in modeling efforts.

biomass burning↗