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Constraints on chemical evolution models from QSOALS abundances

Models of the formation and early chemical evolution of our Galaxy are guided and constrained by our knowledge of abundances in globular cluster stars and halo field stars. The abundance patterns identified in halo and disk stars should be discernible in absorption lines of gas clouds in forming galaxies which are accidentally lying in front of background QSO's. Conversely, the ensemble of QSO absorption line systems (QSOALS) at each redshift may suggest a detailed model for the formation of our Galaxy that is testable using abundance patterns in halo stars.

Lauroesch, J. T.

Chemical evolution of dense clouds

Chemical processes that could determine the molecular composition of the cloud during the several stages of its evolution are considered. Reactions at the relatively interstellar densities are emphasized.

Chappelle, E. W.

Chemical evolution of the Earth: Equilibrium or disequilibrium process?

To explain the apparent chemical incompatibility of the Earth's core and mantle or the disequilibrium process, various core forming mechanisms have been proposed, i.e., rapid disequilibrium sinking of molten iron, an oxidized core or protocore materials, and meteorite contamination of the upper mantle after separation from the core. Adopting concepts used in steady state thermodynamics, a method is devised for evaluating how elements should distribute stable in the Earth's interior for the present gradients of temperature, pressure, and gravitational acceleration. Thermochemical modeling gives useful insights into the nature of chemical evolution of the Earth without overly speculative assumptions. Further work must be done to reconcile siderophile elements, rare gases, and possible light elements in the outer core.

Sato, M.

Analytic models of the chemical evolution of galaxies

Techniques are described for constructing analytic models of the chemical evolution of galaxies subject to infall of metal-poor material onto a maturing disk. A class of linear models is discussed which takes the star-formation rate within a defined region to be proportional to the mass of interstellar gas within that region, and the instantaneous recycling approximation is adopted. The solutions are obtained by approximately matching the infall rate to parametrized familiies of functions for which the equations are exactly soluble. The masses, the primary and secondary metallicities, and the gas concentrations of radioactive chronometers can all then be analytically expressed. Surveys of galactic abundances in location and in time can be compared to the parameter spaces of the analytic representations.

Clayton, Donald D.

Carbon Monoxide Isotopes: On the Trail of Galactic Chemical Evolution

From the early days of the discovery of radio emission from carbon monoxide it was realized that it offered unusual potential for under- standing the chemical evolution of the Galaxy and external galaxies through measurements of molecular isotopes. These results bear on stellar nucleosynthesis, star formation, and gases in the interstellar medium. Progress in isotopic radio measurements will be reviewed.

isotopes nucleosynthesis

Comets - Chemistry and chemical evolution

Research on the chemical composition and conditions in comets and their possible role in the origin of life on earth is surveyed. The inorganic and organic compounds and ions indicated in the ultraviolet and visible spectra of comets are noted, and evidence for the existence of at least a small proportion of complex organic molecules in comets is presented. It is then pointed out that while cometary material could have reached the earth and provided volatile elements from which biochemical compounds could have formed, it is unlikely that a cometary nucleus could have withstood the temperatures and pressures necessary to sustain an environment in which life could have originated.

Donn, B.

Galactic chemical evolution and nucleocosmochronology - Standard model with terminated infall

Some exactly soluble families of models for the chemical evolution of the Galaxy are presented. The parameters considered include gas mass, the age-metallicity relation, the star mass vs. metallicity, the age distribution, and the mean age of dwarfs. A short BASIC program for calculating these parameters is given. The calculation of metallicity gradients, nuclear cosmochronology, and extinct radioactivities is addressed. An especially simple, mathematically linear model is recommended as a standard model of galaxies with truncated infall due to its internal consistency and compact display of the physical effects of the parameters.

Clayton, D. D.

Synoptic and chemical evolution of the Antarctic vortex in winter and spring, 1987

The dynamical evolution of the vortex at least up to 50 mb is dominated by synoptic scales in the troposphere. In particular, there is a clear response when poleward extension of tropospheric anticyclones from latitudes of 40 and 50 S to 70 and 80 S occurs. This response is evident in isentropic potential vorticity maps, TOMS ozone fields and SAM II polar stratospheric clouds. An important feature of the high latitude Southern Hemisphere lower stratosphere is a transition at potential temperatures in the 390 to 400 K range. This transition, the vortopause, is clearly marked in aircraft profiles of O3, H2O, N2O and ClO at latitudes 68 to 72 S near the Antarctic peninsula, and also cross-sections of potential vorticity and potential temperature; above it, the isopleths are more closely spaced than below it. The aircraft measurements of H2O, O3, NO sub y, N2O, ClO, and whole air data are examined in material coordinates, theta and P sub theta, backed up by trajectory analysis. The evolution of the chemical mixing ratios is examined in these coordinates as a function of time from mid-August to late September. Conclusions are drawn about the rates of change and their causes. The meteorological and aircraft data are examined for evidence of the following kinds of motion with respect to the vortex: ingress of air aloft, subsidence, peeling off of air to lower latitudes, and folding of the vortopause. Conclusions are presented regarding the evidence for a chemical sink of ozone above and below theta = 400 K, and whether the vortex has a mass flow through it, or if the chemical sink operates on a fixed mass of air. Implications for mid-latitudes are briefly considered in the light of the conclusions.

Tuck, A. F.

Atmospheric Transport During the Transport and Chemical Evolution over the Pacific TRACE-P Experiment

Atmospheric transport over the Pacific Basin is described during NASA's Transport and Chemical Evolution Over the Pacific Experiment (TRACE-P) that was conducted between February - April 2001. The mission included extensive chemical sampling from two aircraft based primarily in Hong Kong and Yokota Air Base, Japan. Meteorological conditions during TRACE-P changed rapidly due to the seasonal winter/spring transition and the decay of prolonged ENSO cold phase (La Nina) conditions. To document these changes, TRACE-P was divided into two halves, and mean flow patterns during each half are presented and discussed. Important circulation features are the semi-permanent Siberian anticyclone and transient middle latitude cyclones that form near eastern Asia and then move eastward over the northern Pacific. Five-day backward trajectories from the various flight tracks show that air sampled by the aircraft had been transported from a variety of locations. Some parcels remained over the tropical western North Pacific during the entire period, while other important origins were Southeast Asia, Africa, and central Asia. Patterns of satellite-derived precipitation and lightning are described. TRACE-P occurs during a neutral to weak La Nina period of relatively cold sea surface temperatures in the tropical Pacific. Compared to climatology, the TRACE-P period exhibits deep convection located west of its typical position; however, tropospheric flow patterns do not exhibit a strong La Nina signal. Circulation patterns during TRACE-P are found to be generally similar to those during NASA's PEM WEST-B mission that occurred in the same region during February - March 1994.

Fuelberg, Henry E.

Chemical evolution of dense clouds

Attention is given to chemical processes which could determine the molecular composition of the cloud during the several stages of its evolution, taking into account thermal reactions at the relatively high interstellar densities expected during the processes. The origin of the observed molecules is discussed together with questions of molecular evolution during collapse of the cloud and the role of organic molecules in planetary chemical evolution. A number of experiments are also considered along with the application of the experimental results to cloud equilibrium problems.

Chapelle, E. W.

Structural and chemical evolutions of a magnesium vanadium oxide cathode under electrochemical cycling in magnesium batteries

The design of cathode materials that remain chemically and structurally stable during repetitive ion insertion and extraction poses a significant challenge in developing multivalent batteries. The cycling stability of traditional metal oxide-based cathode is challenged by sluggish diffusion of multivalent cations and parasitic reactivity at interfacial regimes, including the cathode electrolyte interphase layer (CEI). Understanding the reactions at the cathode-electrolyte interface, particularly those induced by non-stoichiometric surface layers, is a crucial design parameter for both cathode materials and electrolytes. Here, in this study, we employed multimodal analysis, including in situ and ex situ X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS) to examine the surface reactions and subsequent structural and chemical evolutions of the CEI on high voltage magnesium vanadium oxide (MgV 2 O 4 ) spinel cathode during the Mg 2+ insertion/extraction processes. The results revealed that the presence of non-stoichiometric surface layers in the magnesium vanadium oxide cathode drive the decomposition of bis(trifluoromethanesulfonyl)imide (TFSI - ) anion, leading to the formation of the CEI layer. The CEI layer could inhibit the Mg 2+ ion transfer processes. Accompanying this reactivity-driven degradation, the magnesium vanadium oxide cathode undergoes pulverization, forming clusters of nanosized particles. This process likely improves cycling ability by creating new intercalation sites and shortening the diffusion pathway for the Mg 2+ cations. This study demonstrates that controlling surface stoichiometry and engineering morphological properties are critical design parameters for high performance cathodes for multivalent batteries.

25 ENERGY STORAGE

The role of cometary particle coalescence in chemical evolution

Important prebiotic organic compounds might have been transported to earth in dust or produced in vapor clouds resulting from atmospheric explosions or impacts of comets. These compounds coalesced in the upper atmosphere with particles ejected from craters formed by impacts of large objects. Coalescence during exposure to UV radiation concentrated organic monomers and enhanced formation of oligomers. Continuing coalescence added material to the growing particles and shielded prebiotic compounds from prolonged UV radiation. These particles settled into the lower atmosphere where they were scavenged by rain. Aqueous chemistry and evaporation of raindrops containing monomers in high temperature regions near the earth's surface also promoted continued formation of oligomers. Finally, these oligomers were deposited in the oceans where continued prebiotic evolution led to the most primitive cell. Results of present studies suggest that prebiotic chemical evolution may be an inevitable consequence of impacting comets during the late accretion of planets anywhere in the universe if oceans remained on those planetary surfaces.

Oberbeck, V. R.

Galactic Chemical Evolution of Short-lived Radioactive Isotopes Produced by Explosive Nucleosynthesis: 60 Fe and 53 Mn

Several short-lived radionuclides (SLRs) are know to have existed in the early solar system (ESS). These species, which typically decay with half-lives of the order of a few million years, can be used to probe the timescales of events preceding the birth of the Sun. We investigate the ESS origin of 53 Mn, produced by core-collapse supernovae (CCSNe) and Type Ia supernovae (SNe Ia), and 60 Fe, produced exclusively by CCSNe. We model the evolution of the radioactive-to-stable abundance ratios of these SLRs with a Galactic chemical evolution (GCE) framework accounting for different SN yields, SN Ia delay times, and other Galactic features (K). A further set of models is calculated assuming that SNe Ia did not contribute any 53 Mn to the ESS. The predicted ratios are compared to meteoritic ratios to derive a distribution of solar isolation times that includes uncertainties due to stochastic chemical enrichment and measurements of the ESS values. The isolation times are then compared to those of 107 Pd and 182 Hf calculated in previous work. A self-consistent solution can be found within the current uncertainties, especially when using the GCE setups with K = 1.6 and 2.3, although the maximum likelihood for the 60 Fe distribution is typically ∼4–5 Myr shorter than for 53 Mn. The predicted 60 Fe/ 53 Mn ratio, instead, is completely inconsistent with the ESS value; this could be resolved using a larger fraction of faint CCSNe than usually considered in GCE models.

79 ASTRONOMY AND ASTROPHYSICS

Galactic chemical evolution with the short-lived isotopes 53 Mn, 60 Fe, 182 Hf, and 244 Pu

We run a three-dimensional Galactic chemical evolution (GCE) model to follow the propagation of 53 Mn from supernovae of type Ia (SNIa), 60 Fe from core-collapse supernovae (CCSNe), 182 Hf from intermediate mass stars (IMSs), and 244 Pu from neutron star mergers (NSMs) in the Galaxy. We compare the GCE of these short-lived radioactive isotopes (SLRs) to recent detections on the deep-sea floor. We find that although these SLRs originate from different sites, they often arrive conjointly on Earth.

79 ASTRONOMY AND ASTROPHYSICS

Reactive Nitrogen in Asian Continental Outflow over the Western Pacific: Results from the NASA Transport and Chemical Evolution over the Pacific (TRACE-P)Airborne Mission

We present here results for reactive nitrogen species measured aboard the NASA DC-8 aircraft during the Transport and Chemical Evolution over the Pacific TRACE-P) mission. The large-scale distributions total reactive nitrogen (NO(sub y,sum) = NO + NO2 + HNO3 + PAN + C(sub 1)-C(sub 5) alkyl nitrates) and O3 and CO were better defined in the boundary layer with significant degradation of the relationships as altitude increased. Typically, NO(sub y,sum) was enhanced over background levels of approx.260 pptv by 20-to-30-fold. The ratio C2H2/CO had values of 1-4 at altitudes up to 10 km and as far eastward as 150degE, implying significant vertical mixing of air parcels followed by rapid advection across the Pacific. Analysis air parcels originating from five principal Asian source regions showed that HNO3 and PAN dominated NO(sub y,sum). Correlations of NO(sub y,sum) with C2Cl4 (urban tracer) were not well defined in any of the source regions, and they were only slightly better with CH3Cl (biomass tracer). Air parcels over the western Pacific contained a complex mixture of emission sources that are not easily resolvable as shown by analysis of the Shanghai mega-city plume. It contained an intricate mixture of pollution emissions and exhibited the highest mixing ratios of NO(sub y,sum) species observed during TRACE-P. Comparison of tropospheric chemistry between the earlier PEM-West B mission and the recent TRACE-P data showed that in the boundary layer significant increases in the mixing ratios of NO(sub y,sum)species have occurred, but the middle and upper troposphere seems to have been affected minimally by increasing emissions on the Asian continent over the last 7 years.

Talbot, R.

The chemical evolution of molecular clouds

The nonequilibrium chemistry of dense molecular clouds (10,000 to 1 million hydrogen molecules per cu cm) is studied in the framework of a model that includes the latest published chemical data and most of the recent theoretical advances. In this model the only important external source of ionization is assumed to be high-energy cosmic-ray bombardment; standard charge-transfer reactions are taken into account as well as reactions that transfer charge from molecular ions to trace-metal atoms. Schemes are proposed for the synthesis of such species as NCO, HNCO, and CN. The role played by adsorption and condensation of molecules on the surface of dust grains is investigated, and effects on the chemical evolution of a dense molecular cloud are considered which result from varying the total density or the elemental abundances and from assuming negligible or severe condensation of gaseous species on dust grains. It is shown that the chemical-equilibrium time scale is given approximately by the depletion times of oxygen and nitrogen when the condensation efficiency is negligible; that this time scale is probably in the range from 1 to 4 million years, depending on the elemental composition and initial conditions in the cloud; and that this time scale is insensitive to variations in the total density.

Iglesias, E.