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At least 19 records

The role of molecular hydrogen and methane oxidation in the water vapour budget of the stratosphere

The detailed photochemistry of methane oxidation has been studied in a coupled chemical/dynamical model of the middle atmosphere. The photochemistry of formaldehyde plays an important role in determining the production of water vapor from methane oxidation. At high latitudes, the production and transport of molecular hydrogen is particularly important in determining the water vapor distribution. It is shown that the ratio of the methane vertical gradient to the water vapor vertical gradient at any particular latitude should not be expected to be precisely 2, due both to photochemical and dynamical effects. Modeled H2O profiles are compared with measurements from the Limb Infrared Monitor of the Stratosphere (LIMS) experiment at various latitudes. Molecular hydrogen is shown to be responsible for the formation of a secondary maximum displayed by the model water vapor profiles in high latitude summer, a feature also found in the LIMS data.

Le Texier, H.↗

Increasing CO2 Coupled with Other Anthropogenic Perturbations: Effects on Ozone and Other Trace Gases

The GSFC 2D interactive chemistry-radiation-dynamics model has been used to study the effects on stratospheric trace gases of past and future CO2 increases coupled with changes in CFC'S, methane, and nitrous oxide. Previous simulations with the GSFC model showed that the stratospheric cooling calculated to result from doubling atmospheric CO2 would lead, in the absence of a growth of other anthropogenic gases, to a decrease in upper stratospheric NO(y) of roughly 15%. This work has been extended to simulate changes in stratospheric chemistry and dynamics occurring between the years 1960 and 2050. The simulations have been carried out with and without changes in CO2. In the low latitude upper stratosphere ozone is predicted to be 10% greater in 2050 than in 1990 when increased CO2 is included, compared with an increase of only 2% without the inclusion of CO2. In the low latitude lower stratosphere, ozone is predicted to decrease by about 1% between 1990 and 2050 when CO2 changes are taken into account, in contrast to an approximate 3% increase when they are not. The simulated behavior of water vapor is another example of the coupled responses. Between 1990 and 2050 low latitude water vapor is predicted to increase by 4% and 2% in the upper and lower stratosphere, respectively, without the inclusion of CO2 increases. with the inclusion of CO2 changes, the water vapor increases are predicted to be roughly 12% and 8%, for the upper and lower stratosphere, respectively.

Rosenfield, J. E.↗

Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants

Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration, (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control, and (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

Ollis, David F.↗

Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants

Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

Ollis, David F.↗

Methane Sensitivity to Perturbations in Tropospheric Oxidizing Capacity

Methane is an important greenhouse gas and has a 25 times greater global warming potential than CO2 on a century timescale. Yet there are considerable uncertainties in the magnitude and variability of its sources and sinks. The response of the coupled non-linear methane-carbon monoxide-hydroxyl radical (OH) system is important in determining the tropospheric oxidizing capacity. Using the NASA Goddard Earth Observing System, Version 5 (GEOS-5) chemistry climate model, we study the response of methane to perturbations of OH and wetland emissions. We use a computationally-efficient option of the GEOS-5 CCM that includes an OH parameterization that accurately represents OH predicted by a full chemical mechanism. The OH parameterization allows for studying non-linear CH4-CO-OH feedbacks in computationally fast sensitivity experiments. We compare our results with surface observations (GMD) and discuss the range of uncertainty in OH and wetland emissions required to bring modeling results in better agreement with surface observations. Our results can be used to improve projections of methane emissions and methane growth.

Yegorova, Elena↗

Use of Molecular Fossils for the Interpretation of Paleoenvironments on Early Earth: The Synthesis of Lipid Biomarkers by Methane-Oxidizing Bacteria

Over the course of Earth's history, the most important biological influence has come from the evolution of oxygenic photosynthesis and the development of an oxygen-rich biosphere. Although the availability of free oxygen had profound effects on subsequent biological and planetary evolution, clear paleobiological evidence of the timing of this transition is lacking. Recent technical advances in the microanalysis of organic matter has made it possible to detect residual molecules (biomarkers) in proterozoic (2.5 to 0.6 billion years) sedimentary rock characteristic of specific groups of microorganisms. When coupled with the carbon isotopic fractionations characteristic of biological systems and the new field of compound specific isotope analysis, biomarkers could prove to be a powerful tool for decoding ancient biochemistry from the geological record. We have been studying the carbon isotope fractionations associated with the synthesis of organic biomarker molecules in several types of methane-oxidizing bacteria that should have been key to carbon cycling in paleoenvironments after the evolution of oxygenic photosynthesis.

Jahnke, Linda L.↗

Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

Jachimowski, C. 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.↗

Ozone Sensitivity to Varying Greenhouse Gases and Ozone-Depleting Substances in CCMI-1 Simulations

Ozone fields simulated for the first phase of the Chemistry-Climate Model Initiative (CCMI-1) will be used as forcing data in the 6th Coupled Model Intercomparison Project. Here we assess, using reference and sensitivity simulations produced for CCMI-1, the suitability of CCMI-1 model results for this process, investigating the degree of consistency amongst models regarding their responses to variations in individual forcings. We consider the influences of methane, nitrous oxide, a combination of chlorinated or brominated ozone-depleting substances, and a combination of carbon dioxide and other greenhouse gases. We find varying degrees of consistency in the models' responses in ozone to these individual forcings, including some considerable disagreement. In particular, the response of total-column ozone to these forcings is less consistent across the multi-model ensemble than profile comparisons. We analyse how stratospheric age of air, a commonly used diagnostic of stratospheric transport, responds to the forcings. For this diagnostic we find some salient differences in model behaviour, which may explain some of the findings for ozone. The findings imply that the ozone fields derived from CCMI-1 are subject to considerable uncertainties regarding the impacts of these anthropogenic forcings. We offer some thoughts on how to best approach the problem of generating a consensus ozone database from a multi-model ensemble such as CCMI-1.

CCMI↗

Methane production and consumption in grassland and boreal ecosystems

The objectives of the this project were to develop a mechanistic understanding of methane production and oxidation suitable for incorporation into spatially explicit models for spatial extrapolation. Field studies were undertaken in Minnesota, Canada, and Colorado to explore the process controls over the two microbial mediated methane transformations in a range of environments. Field measurements were done in conjunction with ongoing studies in Canada (the Canadian Northern Wetlands Projects: NOWES) and in Colorado (The Shortgrass Steppe Long Term Ecological Research Project: LTER). One of the central hypotheses of the proposal was that methane production should be substrate limited, as well as being controlled by physical variables influencing microbial activity (temperature, oxidation status, and pH). Laboratory studies of peats from Canada and Minnesota (Northern and Southern Boreal) were conducted with amendments of a methanogenic substrate at multiple temperatures and at multiple pHs (the latter by titrating samples). The studies showed control by substrate, pH, and temperature in order in anaerobic samples. Field and laboratory manipulations of natural plant litter, rather than an acetogenic substrate, showed similarly large effects. The studies concluded that substrate is an important control over methanogenesis, that substrate availability in the field is closely coupled to the chemistry of the dominant vegetation influencing its decomposition rate, that most methane is produced from recent plant litter, and that landscape changes in pH are an important control, highly correlated with vegetation.

Schimel, David S.↗

The potential impact on atmospheric ozone and temperature of increasing trace gas concentrations

The response of the atmosphere to emissions of chlorofluorocarbons (CFCs) and other chlorocarbons, and to increasing concentrations of other radiatively active trace gases such as CO2, CH4, and N2O is calculated by a coupled chemical-radiative transport one-dimensional model. It is shown that significant reductions in the ozone concentration and in the temperature are expected in the upper stratosphere as a result of increasing concentrations of active chlorine produced by photodecomposition of the CFCs. The ozone content is expected to increase in the troposphere, as a consequence of increasing concentrations of methane and nitrogen oxides. Due to enhanced greenhouse effects, the Earth's surface should warm up by several degrees. The amplitude and even the sign of future changes in the ozone column are difficult to predict as they are strongly scenario-dependent. An early detection system to prevent noticeable ozone changes as a result of increasing concentrations of source gases should thus be based on a continuous monitoring of the ozone amount in the upper stratosphere rather than on measurements of the ozone column only. Measurements of NOx, Clx, and HOx are also required for unambiguous trend detection and interpretation.

Brasseur, G.↗

A two-dimensional model with coupled dynamics, radiative transfer, and photochemistry. 2: Assessment of the response of stratospheric ozone to increased levels of CO2, N2O, CH4, and CFC

The impact of increased levels of carbon dioxide (CO2), chlorofluorocarbons (CFCs), and other trace gases on stratospheric ozone is investigated with an interactive, two-dimensional model of gas phase chemistry, dynamics, and radiation. The scenarios considered are (1) a doubling of the CO2 concentration, (2) increases of CFCs, (3) CFC increases combined with increases of nitrous oxide (N2O) and methane CH4, and (4) the simultaneous increase of CO2, CFCs, N2O, and CH4. The radiative feedback and the effect of temperature and circulation changes are studied for each scenario. For the double CO2 calculations the tropospheric warming was specified. The CO2 doubling leads to a 3.1% increase in the global ozone content. Doubling of the CO2 concentrations would lead to a maximum cooling of about 12 C at 45 km if the ozone concentration were held fixed. The cooling of the stratosphere leads to an ozone increase with an associated increase in solar heating, reducing the maximum temperature drop by about 3 C. The CFC increase from continuous emissions at 1985 rate causes a 4.5% loss of ozone. For the combined perturbations a net loss of 1.3% is calculated. The structure of the perturbations shows a north-south asymmetry. Ozone losses (when expressed in terms of percent changes) are generally larger in the high latitudes of the southern hemisphere as a result of the eddy mixing being smaller than in the northern hemisphere. Increase of chlorine leads to ozone losses above 30 km altitude where the radiative feedback results in a cooler temperature and an ozone recovery of about one quarter of the losses predicted with a noninteractive model. In all the cases, changes in circulation are small. In the chlorine case, circulation changes reduce the calculated column depletion by about one tenth compared to offline calculations.

Schneider, Hans R.↗

Linkages Between Ozone-depleting Substances, Tropospheric Oxidation and Aerosols

Coupling between the stratosphere and the troposphere allows changes in stratospheric ozone abundances to affect tropospheric chemistry. Large-scale effects from such changes on chemically produced tropospheric aerosols have not been systematically examined in past studies. We use a composition-climate model to investigate potential past and future impacts of changes in stratospheric ozone depleting substances (ODS) on tropospheric oxidants and sulfate aerosols. In most experiments, we find significant responses in tropospheric photolysis and oxidants, with small but significant effects on methane radiative forcing. The response of sulfate aerosols is sizeable when examining the effect of increasing future nitrous oxide (N2O) emissions. We also find that without the regulation of chlorofluorocarbons (CFCs) through the Montreal Protocol, sulfate aerosols could have increased by 2050 by a comparable amount to the decreases predicted due to relatively stringent sulfur emissions controls. The individual historical radiative forcings of CFCs and N2O through their indirect effects on methane (−22.6mW/sq. m for CFCs and −6.7mW/sq. m for N2O) and sulfate aerosols (−3.0mW/sq. m for CFCs and +6.5mW/sq. m for N2O when considering the direct aerosol effect) discussed here are non-negligible when compared to known historical ODS forcing. Our results stress the importance of accounting for stratosphere-troposphere, gas-aerosol and composition-climate interactions when investigating the effects of changing emissions on atmospheric composition and climate.

troposphere↗

Airborne Measurements of Western U.S. Wildfire Emissions: Comparison with Prescribed Burning and Air Quality Implications

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total non methane organic compounds, and PM1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM1 emission estimate (1530 +/- 570 Gg/yr) is over 3 times that of the NEI PM2.5 estimate and is also higher than the PM2.5 emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions.

measured oxygenated volatile organic compounds↗

Concentration Field of Reactants and Products Species in a Reacting Vortex Ring

The proposed paper will present experimental and numerical results on the concentration fields of both reactants and products species in a reacting vortex ring that is generated from the interaction between a diffusion flame and a laminar vortex ring. Flame-vortex interactions are canonical configurations used to study the underlying processes occurring in complicated turbulent reacting flows. This type of configuration contains many of the fundamental aspects of the coupling between fluid dynamics and combustion that could be investigated with more controllable conditions than are possible under direct investigations of turbulent flames. The current configuration has been studied experimentally by Chen and Dahm and Chen et al. under microgravity conditions, and by Park and Shin, and You et al. under normal gravity conditions. This configuration is similar to that used in the analyses of Karagozian and Manda of their 2-D vortex pair in which both fuel and entrained oxidizer are present. The vortex ring used in this study is generated by issuing methane into an air environment through the exit of an axisymmetric nozzle. The experiments were conducted under microgravity conditions in order to remove the undesirable effects of buoyancy that can affect both the flame structure and ring dynamics resulting in possibly asymmetric and nonrepeatable interactions. The experimental technique of diode laser wavelength modulation spectroscopy (WMS) is used to measure concentration fields of reactants, CH4 and O2, products, H2O, CO2, OH, and temperature fields which can be inferred from either line pairs of O2 or OH lines. This technique has been investigated previously by Silver and Bomse et al. This is the first time that the technique has been applied to reacting vortex rings under microgravity conditions. The effect of ring circulation and fuel volume on the species concentration fields will be investigated. The experimental results will be compared to the current numerical results, and used to validate the numerical studies. In addition, the existence of burned cores during the interactions will be determined, and the increase in reactant consumption with increased ring circulation will be examined. Numerical studies were also conducted by solving the Navier-Stokes and mixture fraction equations with the assumptions of unity Lewis and Schmidt numbers. Equilibrium chemistry and flamelet libraries were used to obtain the temperature and species mass fraction fields. The numerical results will serve as guidelines in conducting the experimental studies. Ring circulation and fuel volume effects on the interactions and species concentration fields will be investigated and compared to experimental results.

Chen, Shin-Juh↗

Gaseous emissions from Canadian boreal forest fires

CO2-normalized emission ratios for carbon monoxide (CO), hydrogen (H2), methane (CH4), total nonmethane hydrocarbons (TNMHC), and nitrous oxide (N2O) were determined from smoke samples collected during low-altitude helicopter flights over two prescribed fires in northern Ontario, Canada. The emission ratios determined from these prescribed boreal forest fires are compared to emission ratios determined over two graminoid (grass) wetlands fires in central Florida and are found to be substantially higher (elevated levels of reduced gas production relative to CO2) during all stages of combustion. These results argue strongly for the need to characterize biomass burning emissions from the major global vegetation/ecosystems in order to couple combustion emissions to their vegetation/ecosystem type.

Cofer, Wesley R., III↗

Xenon Fractionation, Hydrogen Escape, and the Oxidation of the Earth

Xenon in Earth's atmosphere is severely mass fractionated and depleted compared to any plausible solar system source material, yet Kr is unfractionated. These observations seem to imply that Xe has escaped from Earth. But to date no process has been identified that can cause Xe, which is heavier than Kr, to escape while Kr does not. Vigorous hydrodynamic hydrogen escape can produce mass fractionation in heavy gases. The required hydrogen flux is very high but within the possible range permitted by solar Extreme Ultraviolet radiation (EUV, which here means radiation at wavelengths short enough to be absorbed efficiently by hydrogen) heating when Earth was on the order of 100 Myrs old or younger. However this model cannot explain why Xe escapes but Kr does not. Recently, what appears to be ancient atmospheric xenon has been recovered from several very ancient (3-3.5 Ga) terrestrial hydrothermal barites and cherts. What is eye-catching about this ancient Xe is that it is less fractionated that Xe in modern air. In other words, it appears that a process was active on Earth some 3 to 3.5 billion years ago that caused xenon to fractionate. By this time the Sun was no longer the EUV source that it used to. If xenon was being fractionated by escape — currently the only viable hypothesis — it had to be in the less unfamiliar context of Earth’s Archean atmosphere and under rather modest levels of EUV forcing. This requires a new model. Here we address the circumstances in which Xe, but not Kr, could escape from Earth as an ion. In a hydrodynamically escaping hydrogen wind the hydrogen is partially photo-ionized. The key concepts are that ions are much more strongly coupled to the escaping flow than are neutrals (so that a relatively modest flow of H and H+ to space could carry Xe+ along with it), and that xenon alone among the noble gases is more easily ionized than hydrogen. This sort of escape is possible if not prevented by a planetary magnetic field. The best prospects for Earth are therefore escape along the polar field lines, although a very weak or absent magnetic field would likely work as well. As applied to the Archean Earth the discussion will be constrained by diffusion-limited hydrogen escape. The extended history of hydrogen escape implicit in Xe escape in the Archean is consistent with suggestions that hydrogen escape from the anoxic Archean atmosphere was considerable, because biogenic methane is expected to have been rather abundant. Hydrogen escape plausibly played the key role in creating oxidizing condition at the surface of the Earth and setting the stage for the creation of an O2 atmosphere.

photo-ionized gases↗

Attribution of Stratospheric and Tropospheric Ozone Changes Between 1850 and 2014 in CMIP6 Models

We quantify the impacts of halogenated ozone-depleting substances (ODSs), greenhouse gases (GHGs), and short-lived ozone precursors on ozone changes between 1850 and 2014 using single-forcing perturbation simulations from several Earth system models with interactive chemistry participating in the Coupled Model Intercomparison Project Aerosol and Chemistry Model Intercomparison Project. We present the responses of ozone to individual forcings and an attribution of changes in ozone columns and vertically resolved stratospheric and tropospheric ozone to these forcings. We find that whilst substantial ODS-induced ozone loss dominates the stratospheric ozone changes since the 1970s, in agreement with previous studies, increases in tropospheric ozone due to increases in short-lived ozone precursors and methane since the 1950s make increasingly important contributions to total column ozone (TCO) changes. Increases in methane also lead to substantial extra-tropical stratospheric ozone increases. Impacts of nitrous oxide and carbon dioxide on stratospheric ozone are significant but their impacts on TCO are small overall due to several opposing factors and are also associated with large dynamical variability. The multi-model mean (MMM) results show a clear change in the stratospheric ozone trends after 2000 due to now declining ODSs, but the trends are generally not significantly positive, except in the extra-tropical upper stratosphere, due to relatively small changes in forcing over this period combined with large model uncertainty. Although the MMM ozone compares well with the observations, the inter-model differences are large primarily due to the large differences in the models' representation of ODS-induced ozone depletion.

Halogenated ozone-depleting substances↗