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Photochemistry of interstellar molecules

The photochemistry of two diatomic and eight polyatomic molecules is discussed quantitatively. For an interstellar molecule, the lifetime against photodecomposition depends upon the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. The constant energy density of Habing is used for the unobserved regions of interstellar radiation field, and the field in obscuring clouds is estimated by combining the constant flux with the observed interstellar extinction curve covering the visible and ultraviolet regions. Lifetimes against photodecomposition in the unobscured regions and as a function of increasing optical thickness in obscuring clouds are calculated for the ten species. The results show that, except for CO, all the molecules have comparable lifetimes of less than one hundred years. Thus they can exist only in dense clouds and can never have been exposed to the unobscured radiation. The calculations further show that the lifetimes in clouds of moderate opacity are of the order of one million years.

Stief, L. J.↗

The atmospheric lifetime experiment. I - Introduction, instrumentation, and overview

The Atmospheric Lifetime Experiment is designed to determine accurately the atmospheric concentrations of the four halocarbons CFCl3, CF2Cl2, CCl4, and CH3CCl3, and also of N2O with emphasis on measurement of their long-term trends in the atmosphere. Comparison of these concentrations and trends for the four halocarbons with estimates of their industrial emission rates then enables calculations of their global circulation rates and globally averaged atmospheric lifetimes. The experiment utilizes automated dual-column electron-capture gas chromatographs which sample the background air about 4 times daily at the following globally distributed sites: Adrigole, Ireland, Cape Meares, Oregon; Ragged Point, Barbados; Point Matatula, American Samoa, and Cape Grim, Tasmania. The climatology of these 'clean air' sites and their ability to describe the global air mass are reviewed. The instrumentation and methods for data acquisition and processing are then described. An overview of the data obtained and the trends derived during the 3-year period from July 1978 through June 1981 for each of the five species being measured is presented.

Prinn, R. G.↗

Analysis of Present Day and Future OH and Methane Lifetime in the ACCMIP Simulations

Results from simulations performed for the Atmospheric Chemistry and Climate Modeling Intercomparison Project (ACCMIP) are analysed to examine how OH and methane lifetime may change from present day to the future, under different climate and emissions scenarios. Present day (2000) mean tropospheric chemical lifetime derived from the ACCMIP multi-model mean is 9.8+/-1.6 yr (9.3+/-0.9 yr when only including selected models), lower than a recent observationally-based estimate, but with a similar range to previous multi-model estimates. Future model projections are based on the four Representative Concentration Pathways (RCPs), and the results also exhibit a large range. Decreases in global methane lifetime of 4.5 +/- 9.1% are simulated for the scenario with lowest radiative forcing by 2100 (RCP 2.6), while increases of 8.5+/-10.4% are simulated for the scenario with highest radiative forcing (RCP 8.5). In this scenario, the key driver of the evolution of OH and methane lifetime is methane itself, since its concentration more than doubles by 2100 and it consumes much of the OH that exists in the troposphere. Stratospheric ozone recovery, which drives tropospheric OH decreases through photolysis modifications, also plays a partial role. In the other scenarios, where methane changes are less drastic, the interplay between various competing drivers leads to smaller and more diverse OH and methane lifetime responses, which are difficult to attribute. For all scenarios, regional OH changes are even more variable, with the most robust feature being the large decreases over the remote oceans in RCP8.5. Through a regression analysis, we suggest that differences in emissions of non-methane volatile organic compounds and in the simulation of photolysis rates may be the main factors causing the differences in simulated present day OH and methane lifetime. Diversity in predicted changes between present day and future OH was found to be associated more strongly with differences in modelled temperature and stratospheric ozone changes. Finally, through perturbation experiments we calculated an OH feedback factor (F) of 1.24 from present day conditions (1.50 from 2100 RCP8.5 conditions) and a climate feedback on methane lifetime of 0.33+-0.13 yr/K, on average. Models that did not include interactive stratospheric ozone effects on photolysis showed a stronger sensitivity to climate, as they did not account for negative effects of climate-driven stratospheric ozone recovery on tropospheric OH, which would have partly offset the overall OH/methane lifetime response to climate change.

atmospheric composition↗

Intergenerational Inequities in Exposure to Climate Extremes: Young Generations Are Severely Threatened By Climate Change

Under continued global warming, extreme events such as heat waves will continue to rise in frequency, intensity, duration, and spatial extent over the next decades. Younger generations are therefore expected to face more such events across their lifetimes compared with older generations. This raises important issues of solidarity and fairness across generations that have fueled a surge of climate protests led by young people in recent years and that underpin issues of intergenerational equity raised in recent climate litigation. However, the standard scientific paradigm is to assess climate change in discrete time windows or at discrete levels of warming, a “period” approach that inhibits quantification of how much more extreme events a particular generation will experience over its lifetime compared with another. By developing a “cohort” perspective to quantify changes in lifetime exposure to climate extremes and compare across generations (see the first figure), we estimate that children born in 2020 will experience a two- to sevenfold increase in extreme events, particularly heat waves, compared with people born in 1960, under current climate policy pledges. Our results highlight a severe threat to the safety of young generations and call for drastic emission reductions to safeguard their future. Meteorological extremes, hazards, or climate change impacts are mostly studied as they evolve over time under varying emission scenarios and socioeconomic pathways. For example, applying a heat wave indicator (see table S1) to four bias-adjusted global climate models indicates that the land area annually affected by such heat waves will increase from ~15% around 2020 to ~22% by 2100 under a scenario compatible with limiting global warming to 1.5°C, and to ~46% under a scenario in line with current emission reduction pledges (see the first figure). Recent studies extended this approach, studying aspects of climate change as a function of global mean temperature (GMT) increments, highlighting the scenario-independence of several extreme event indicators but remaining, in essence, a comparison of time windows. By contrast, we performed a birth cohort analysis by combining a collection of multimodel extreme event projections with country-scale life expectancy information, gridded population data, and future global temperature trajectories from the Intergovernmental Panel on Climate Change (IPCC) Special Report on Global Warming of 1.5°C (see supplementary materials). By integrating the exposure of an average person in a country or region to extreme events across their lifetime, we encapsulate spatiotemporal changes in climate hazards, population density, cohort size, and life expectancy (see the first figure).

global warming↗

Estimating the Reliability of Electronic Parts in High Radiation Fields

Radiation effects on materials and electronic parts constrain the lifetime of flight systems visiting Europa. Understanding mission lifetime limits is critical to the design and planning of such a mission. Therefore, the operational aspects of radiation dose are a mission success issue. To predict and manage mission lifetime in a high radiation environment, system engineers need capable tools to trade radiation design choices against system design and reliability, and science achievements. Conventional tools and approaches provided past missions with conservative designs without the ability to predict their lifetime beyond the baseline mission.This paper describes a more systematic approach to understanding spacecraft design margin, allowing better prediction of spacecraft lifetime. This is possible because of newly available electronic parts radiation effects statistics and an enhanced spacecraft system reliability methodology. This new approach can be used in conjunction with traditional approaches for mission design. This paper describes the fundamentals of the new methodology.

radiation↗

Detailed Design and Cost Estimation of a 300 MWe Oxy-Fuel sCO2 Turbine

The detailed design of a 300 MWe, utility scale oxy-fuel turbine has been completed for purposed operation in the sCO2 direct fired Allam-Fetvedt cycle, targeting near-zero emissions and a 50% LHV system efficiency. The turbine and its supporting plant aim to offer a lower levelized cost of energy than a natural gas combined cycle plant employing carbon capture. The oxy-fuel turbine conditions include an inlet temperature of 1150°C and inlet pressure of 305 bar, representing temperatures near that of a gas turbine simultaneously with pressures near an ultra-supercritical steam turbine. The combustor housing and turbine designs were completed according to the ASME BPVC; the turbine case specifically incorporates a multi-body design with inner high-pressure barrel case and low-pressure (30 bar) horizontally split outer case of low-chromium steel material. Lateral rotordynamic evaluation demonstrated acceptable vibration response for a range of imbalance conditions per API standards. The cooling flow required in the six-stage turbine flowpath for 30,000 hr. blade and stator lifetime is predicted through thermal and structural modeling of the first stage. The provided cost estimate of the turbine is formed through a combination of scaled up-costs from procured 10 MWe scale sCO2 turbomachinery hardware, and vendor provided budgetary quotes of larger components including the turbine case requiring casting, welding, and final machining processes. The performance and cost estimation of the oxy-fuel turbine predicted for the completed detailed design provides important information towards future development needs for market penetration of utility scale direct fired sCO2 power cycles.

Marshall, Michael [Southwest Research Institute, S↗

Relationship between the Fluorescence Lifetime of Chlorophyll 'a' and Primary Productivity within the Mississippi River Plume and Adjacent Shelf Region

In situ measurements of chlorophyll fluorescence intensity have been widely used to estimate phytoplankton biomass. However, because the fluorescence quantum yield of chlorophyll a in vivo can be highly variable, measurements of chlorophyll fluorescence intensity cannot be directly correlated with phytoplankton biomass and do not provide information on the physiological state of the phytoplankton under study. Conversely, lifetime-based measurements of chlorophyll fluorescence provide a framework in which photosynthetic rates of phytoplankton can be analyzed according to phytoplankton physiology. Along with the measurement of primary production and ambient nutrient concentrations within the Mississippi River plume in the northern Gulf of Mexico, phytoplankton fluorescence lifetimes were measured using a Fluorescence Lifetime Phytoplankton Analyzer (developed under a NASA Small Business Innovative Research contract to Ciencia, Inc.). Variability of fluorescence lifetimes within the plume can be used as a background from which to interpret variations in the maximum quantum yield of photochemistry. The extent to which nutrient and effluent loading in this dynamic coastal area affect the photosynthetic performance of phytoplankton will be presented as a function of phytoplankton fluorescence lifetimes.

Hall, Callie↗

The Impact of New Estimates of Mixing Ratio and Flux-based Halogen Scenarios on Ozone Evolution

The evolution of ozone in the 21st century has been shown to be mainly impacted by the halogen emissions scenario and predicted changes in the circulation of the stratosphere. New estimates of mixing ratio and flux-based emission scenarios have been produced from the SPARC Lifetime Assessment 2013. Simulations using the Goddard Earth Observing System Chemistry-Climate Model (GEOSCCM) are conducted using this new A1 2014 halogen scenario and compared to ones using the A1 2010 scenario. This updated version of GEOSCCM includes a realistic representation of the Quasi-Biennial Oscillation and improvements related to the break up of the Antarctic polar vortex. We will present results of the ozone evolution over the recent past and 21st century to the A1 2010, A1 2014 mixing ratio, and an A1 2014 flux-based halogen scenario. Implications of the uncertainties in these estimates as well as those from possible circulation changes will be discussed.

Chemistry-Climate Models↗

Contributions to the optical linewidth of shallow donor-bound excitonic transition in ZnO

Neutral shallow donors in zinc oxide (ZnO) are spin qubits with optical access via the donor-bound exciton. This spin–photon interface enables applications in quantum networking, memories, and transduction. Essential optical parameters which impact the spin–photon interface include radiative lifetime, optical inhomogeneous and homogeneous linewidth, and optical depth. We study the donor-bound exciton optical linewidth properties of Al, Ga, and In donors in single-crystal ZnO. The ensemble photoluminescence linewidth ranges from 4 to 11 GHz, less than two orders of magnitude larger than the expected lifetime-limited linewidth. The ensemble linewidth remains narrow in absorption through samples with an estimated optical depth up to several hundred. The primary thermal relaxation mechanism is identified and found to have a negligible contribution to the total linewidth at 2 K. We find that inhomogeneous broadening due to the disordered isotopic environment in natural ZnO is significant, contributing 2 GHz. Two-laser spectral hole burning measurements indicate that the dominant mechanism, however, is homogeneous. Despite this broadening, the high homogeneity, large optical depth, and potential for isotope purification indicate that the optical properties of the ZnO donor-bound exciton are promising for a wide range of quantum technologies, and motivate a need to improve the isotope and chemical purity of ZnO for quantum technologies.

Niaouris, Vasileios (ORCID:000000015313748X)↗

Cathodic Protection Modeling for Hanford Underground Double-Shell Tank Farms

Hanford stores millions of gallons of radioactive and chemically hazardous waste from the production of weapon materials in tank farms consisting of underground carbon-steel storage tanks surrounded by reinforced concrete. Six of these Hanford tank farms use double-shell storage tanks (DSTs). The DST farms were constructed from 1968 to 1986 with a planned 40–50 year design life, so some are already operating beyond their initial life expectancy. Ultrasonic testing (UT) has indicated significant thinning on the bottom of the secondary (outer) liner of these tanks, believed to arise from groundwater intrusion driving concrete side corrosion. There is no direct access to the steel/concrete interface between the tank and the concrete pad, making it difficult to apply a chemical-based mitigation strategy or to conduct repairs, but cathodic protection (CP) is a possible method to inhibit further concrete-side corrosion. Hanford already uses CP to protect below grade steel piping within the tank farms and connected to the tanks, but this system was not designed to protect the tank bottoms. CP design must account for the structures surrounding the DSTs, including the steel reinforcing bars (rebar) within the concrete pad and vault, various process lines, and the existing CP system. In this study, finite element analysis (FEA) modeling was carried out to simulate CP protection of 1) a single tank and CP anode to develop options for modeling the rebar and to compare to a simpler circuit model and 2) the entire Hanford AN tank farm as a representative example consisting of seven tanks, associated piping, and both existing and new CP anodes. Both circuit and FEA models predict that significant protective current could be delivered to the bottoms of the tanks with the addition of tank-protection anodes below the depth of the tanks. Simulations with only the existing pipe-protection anodes active confirmed that only a very small current to the tank bottoms is predicted under present conditions. Multiple simplified representations of the dome and wall rebar were tested to reduce the computational complexity of the tank-farm simulations, resulting in modeling the rebar as edge elements with a prescribed effective circumference that matches the real rebar surface area. The geometry of the rebar is also simplified into horizontal hoops around the tank walls and radial rebar over the dome with increased effective circumference to retain the target surface area. This simplification was found to greatly reduce the complexity and solution time of the models without large changes in current distributions, especially to the tank bottom. A range of values were tested for model parameters such as soil and concrete resistivities and polarization resistance to investigate their impact on the current and electric potential distributions. Depending on the parameters used, FEA simulations predict some risk of overprotection, particularly on the piping system; since overprotection can also lead to surface damage associated with hydrogen gas generation at the interface (e.g. hydrogen embrittlement or damage to coatings), this needs to be considered when refining the design of the new CP system. Comparison between the FEA models and the circuit model representation demonstrated that the circuit model could not match the predicted FEA current distribution, even when using the exact same surface areas. This discrepancy appeared to be at least partly attributable to the impact of the relative positions of the tank components and anodes to each other and to the ground surface. The FEA model accounts for the relative positions since it solves the governing equations in three dimensions, but the circuit model cannot account for the positioning. In particular, the circuit model underpredicts the current to the tank bottom and overpredicts the current to the dome compared to FEA for the baseline geometry. The FEA models omitted the electrically isolated rebar in the bottom concrete slab. However, a circuit based stray current model estimated that only 2.1% of the total current through the slab would stray into the rebar, corresponding to ~0.21 A for a target current density of 2 mA/ft2 to the tank bottom. The estimated corrosion driven by this amount of stray current is predicted to yield a lifetime of >400 years for the minimum rebar diameter, assuming an acceptable cross-section area loss of 10%.

d'Entremont, Anna [Savannah River National Laborat↗

Effect of facility background gases on internal erosion of the 30-cm Hg ion thruster

One life limiting phenomenon of mercury bombardment thrusters is sputtering erosion of the upstream side of the molybdenum screen grid by discharge chamber ions. Data were obtained which revealed that the screen grid erosion was very sensitive to the partial pressure of certain background gases in the space simulation vacuum facility. The results of tests conducted to evaluate this effect are presented. An estimate of the screen grid erosion in space was made which showed that adequate lifetime for proposed missions exists.

Rawlin, V. K.↗

On reaction kinetics and atmospheric lifetimes of CF3CFHCF3 and CF3CH2Br

The rate constants for the reaction of the OH radical with CF3CFHCF3 and with CF3CH2Br have been measured as a function of temperature using the discharge flow technique with laser induced fluorescence detection of the OH radicals. The temperature dependent rate coefficients are well described by a simple Arrhenius expression, k(T) = A exp(E/(RT)). For the reaction of OH with CF3CFHCF3 we find A = 3.7 x 10 exp -13 cu cm/molecules/s and E/R = 1615 K; for the reaction of OH with CF3CH2Br we report A = 1.4 x 10 exp -12 cu cm/molecule/s and E/R = 1350 K. These Arrhenius parameters imply rate coefficients at 277 K of 1.09 x 10 exp -15 cu cm/molecule/s for CF3CFHCF3 and 1.06 x 10 exp -14 cu cm/molecule/s for CF3CH2Br. We find atmospheric lifetimes for CF3CFHCH3 and CF3CH2Br of 42 years and 4.1 years, respectively. We also estimate the steady state ozone depletion potential (ODP) of the brominated species relative to CFCl3 as about 0.84 using a semiempirical model.

Nelson, D. D., Jr.↗

The Contemporary Hazard of Cometary Impacts

Cosmic impacts pose a continuing hazard of loss of human life and property. Significant contemporary risk is associated with projectiles in the energy range from about 10 megatons of TNT up to the size of the K/T impactor. The lower threshold for damage is defined by the atmosphere of the Earth, which effectively shields us From smaller projectiles. Up to energies of about a gigaton of TNT, the effects are local or regional for impacts on the land, or coastal for ocean impacts, which can generate large tsunamis. A greater risk is associated with still larger impacts, which are capable of causing global ecological catastrophe, possibly leading to mass mortality From starvation and epidemics. If such a impact took place anywhere on Earth during our lifetimes, we would each be in danger, independent of where the projectile struck. Statistical estimates indicate that each human on this planet runs a risk of roughly 1 in 20,000 of dying from this cause. Prudence suggests that we should be concerned about such impacts and seek ways of avoiding them or mitigating their consequences. The primary objective of any program to deal with this hazard is to determine whether or not such a near-term impact is likely. The best approach for the asteroidal component is a comprehensive telescopic survey, which can discover all Earth-crossing asteroids larger than 1 km in diameter and provide decades of warning in which to plan ways to deflect or destroy a threatening object. Long-period comets, however, pose a much greater challenge, since they cannot be discovered long in advance of a possible impact, their orbits are harder to predict, and they are significantly more difficult to deflect or destroy.

Morrison, David↗

Case Studies of the Vertical Structure of the Direct Shortwave Aerosol Radiative Forcing During TARFOX

The vertical structure of aerosol-induced radiative flux changes in the Earth's troposphere affects local heating rates and thereby convective processes, the formation and lifetime of clouds, and hence the distribution of chemical constituents. We present observationally based estimates of the vertical structure of direct shortwave aerosol radiative forcing for two case studies from the Tropospheric Aerosol Radiative Forcing Observational Experiment (TARFOX) which took place on the U.S. east coast in July 1996. The aerosol radiative forcings are computed using the Fu-Liou broadband radiative transfer model. The aerosol optical properties used in the radiative transfer simulations are calculated from independent vertically resolved estimates of the complex aerosol indices of refraction in two to three distinct vertical layers, using profiles of in situ particle size distributions measured aboard the University of Washington research aircraft. Aerosol single-scattering albedos at 450 nm thus determined range from 0.9 to 0.985, while the asymmetry factor varies from 0.6 to 0.8. The instantaneous shortwave aerosol radiative forcings derived from the optical properties of the aerosols are of the order of -36 Wm(exp -2) at the top of the atmosphere and about -56 Wm(exp -2) at the surface for both case studies.

Redemann, J.↗

Deriving Lifetime Maps in the Time/Frequency Domain of Coherent Structures in the Turbulent Boundary Layer

The lifetimes of coherent structures are derived from data correlated over a 3 sensor array sampling streamwise sidewall pressure at high Reynolds number (> 10(exp 8)). The data were acquired at subsonic, transonic and supersonic speeds aboard a Tupolev Tu-144. The lifetimes are computed from a variant of the correlation length termed the lifelength. Characteristic lifelengths are estimated by fitting a Gaussian distribution to the sensors cross spectra and are shown to compare favorably with Efimtsov s prediction of correlation space scales. Lifelength distributions are computed in the time/frequency domain using an interval correlation technique on the continuous wavelet transform of the original time data. The median values of the lifelength distributions are found to be very close to the frequency averaged result. The interval correlation technique is shown to allow the retrieval and inspection of the original time data of each event in the lifelength distributions, thus providing a means to locate and study the nature of the coherent structure in the turbulent boundary layer. The lifelength data are converted to lifetimes using the convection velocity. The lifetime of events in the time/frequency domain are displayed in Lifetime Maps. The primary purpose of the paper is to validate these new analysis techniques so that they can be used with confidence to further characterize the behavior of coherent structures in the turbulent boundary layer.

Palumbo, Dan↗

Improved semiclassical model for real-time evaporation of matrix black holes

In this paper, we study real-time classical matrix mechanics of a simplified 2 × 2 matrix model inspired by the black hole evaporation problem. This is a step towards making a quantitative model of real-time evaporation of a black hole, which is realized as a bound state of D0-branes in string theory. The model we study is the reduction of Yang–Mills in 2 + 1 dimension to 0 + 1 dimensions, which has been corrected with an additional potential that can be interpreted as a zero-point energy for fermions. Our goal is to understand the lifetime of such a classical bound state object in the classical regime. To do so, we pay particular attention to when D-particles separate to check that the “off-diagonal modes” of the matrices become adiabatic and use that information to improve on existing models of evaporation. It turns out that the naive expectation value of the lifetime with the fermionic correction is infinite. This is a logarithmic divergence that arises from very large excursions in the separation between the branes near the threshold for classical evaporation. The adiabatic behavior lets us get some analytic control of the dynamics in this regime to get this estimate. This divergence is cutoff in the quantum theory due to quantization of the adiabatic parameter, resulting in a long lifetime of the bound state, with a parametric dependence of order log(1/ℏ).

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Assessing Acetone for the GISS ModelE2.1 Earth System Model

Acetone is an abundant volatile organic compound (VOC) in the atmosphere, with important influences on ozone and oxidation capacity. Direct sources include chemical production from other VOCs and anthropogenic emissions, terrestrial vegetation, biomass-burning emissions, and ocean production. Sinks include chemical loss, deposition onto the land surface, and ocean uptake. Acetone also has a lifetime that is long enough to allow transport and reactions with other compounds remote from its sources. The NASA Goddard Institute for Space Studies (GISS) Earth system model ModelE2.1 simulates a variety of Earth system interactions. Previously, acetone had a very simplistic representation in the ModelE chemical scheme. This study assesses a more sophisticated acetone scheme in which acetone is a full 3-dimensional tracer with explicit sources, sinks, and atmospheric transport. We first evaluate the new global acetone budget in the context of past literature. Estimated source and sink fluxes fall within the range of previous models, although total atmospheric burden and lifetime are at the lower end of the published literature. Acetone's new representation in ModelE2.1 also results in more realistic spatial and vertical distributions, which we compare against previous models and field observations. The seasonality of acetone-related processes was also studied in conjunction with field measurements, and these comparisons show promising agreement but also shortcomings at high-emission urban locations, where the model's resolution is too coarse to capture the true behavior. Finally, we conduct a variety of sensitivity studies that explore the influence of key parameters on the acetone budget and its global distribution. An impactful finding is that the production of acetone from precursor hydrocarbon oxidation has strong leverage on the overall chemical source, indicating the importance of accurate molar yields. Overall, our implementation is one that corroborates with previous studies and marks a significant improvement in the development of the acetone tracer in GISS ModelE2.1.

Acetone↗