Gas-Phase Formation of Water-Soluble Organic Compounds in the Atmosphere: A Retrosynthetic Analysis

Atmospheric particles contain a myriad of organiccompounds, including many multifunctional,water-soluble organic compounds. Many of thesecompounds are postulated to be secondary of origin. This work investigates the possible precursors ofseveral classes of multifunctional, water-solublesecondary organic compounds by analyzing the pathwaysleading to their formation, based on known gas-phasereactions. The analysis is termed `retrosynthetic'due to the backward direction of the analysis, fromproducts to precursors. Pathways for multi-functionalcompounds were generated combinatorially, consideringthe formation of one functional group at a time.Many multifunctional organic compounds with carboxylicacid, carbonyl, and hydroxy functional groups werefound to be first- or second-generation products ofcommon anthropogenic and biogenic volatile organiccompounds such as alkanes, alkenes, aromatics, andcyclic alkenes. The estimated yields of water-solubleorganic compounds from primary precursors ranged fromless than 1% to over 10%, based on stoichiometricconsiderations. The SOA formation index, whichcombines the concepts of yields and rates, was used tocompare the feasibility of the retrosyntheticpathways. Many of the candidate pathways involve theisomerization reaction of alkoxy radicals andoxygenated intermediate products such asmonocarboxylic acids and hydroxyaldehydes.     

Carbonate shedding and sedimentary cyclicities of a distally steepened carbonate ramp (Miocene, Great Bahama Bank)

Received: 10 May 1999 / Accepted: 16 October 1999     

Fictive component model of pyroxenes and multicomponent phase equilibria

Pyroxenes are considered as ideal solid solutions of some real components (e.g. diopside or orthoenstatite) and some fictive or hypothetical components (e.g. orthodiopside or orthohedenbergite). Using the reversed experimental data in the CaO-MgO-SiO₂ system, the Gibbs free energy of formation of fictive orthodiopside and of fictive clinoenstatite have been determined in the temperature range of 1,000 to 1,600 °K. The data on free energies of components in the binary system can be used to extend the fictive component model to the ternary CaSiO₃-MgSiO₃-FeSiO₃ system. Using published phase diagrams on the pyroxene quadrilateral, Gibbs free energy of formation of fictive orthohedenbergite has been calculated. Application of the ideally mixing fictive component model to computation of phase equilibria leads to the determination of compositions of coexisting Fe-Mg-Ca pyroxenes at different temperatures.Abbreviations and symbols G _f ⁰ Gibbs free energy of formation from the elements at 1 bar and temperature - G ^Ex excess free energy of mixing in a solution - G molar Gibbs free energy - R gas constant - H enthalpy - S entropy - T absolute temperature - P pressure - KJ/M kilojoules per mole - j joules - Opx orthopyroxene - Cpx clinopyroxene - H hedenbergite - D diopside - E enstatite - F ferrosilite - X mole fraction - K equilibrium constant     

Absolute sea level determination for the subtropical Atlantic Climate Study

The Subtropical Atlantic Climate Study (STACS) is a subprogram in the NOAA climate program designed to access the feasibility of monitoring horizontal fluxes in the Gulf Stream system off Florida. Transport in the Florida Current fluctuates on time scales which are reflected in sea level records monitored at tide gauges. Geodetic leveling, connecting tide gauges along the east coast of the United States, allows intercomparison of sea level records alongstream, but the cross-stream and alongstream records in the Bahamas and Cuba are not connected. In this study, various methods to determine absolute sea level differences across the Straits of Florida between Miami, Florida and Cat Cay, Bahamas, a part of the STACS area, were investigated; the desired accuracy of the sea level difference is ± 1 cm. This study indicates that a combination of dense gravity data with satellite altimeter (TOPEX and GEOSAT) data in the STACS area could provide a ± 1 cm absolute sea level difference accuracy across the Straits of Florida. This paper also provides discussion of other conventional methods.     

Characteristics of turbulent fluxes of sensible heat and momentum in the surface boundary layer during the Indian summer monsoon

Turbulent fluctuations of wind and temperature were measured using a three-component sonic anemometer at 8 m on a 30 m micro-meteorological tower erected at the Indian Institute of Technology (IIT) Kharagpur (22.3° N, 87.2° E), India, as part of the Monsoon Trough Boundary Layer Experiment (MONTBLEX). Diurnal and nocturnal variations of fluxes of sensible heat and momentum were estimated by the eddy correlation technique from 42 observations, each of 10 min duration during 6–8 July in the monsoon season of 1989. The estimated heat flux shows a diurnal trend while the momentum flux shows variability but no particular trend. The nocturnal heat flux changes sign intermittently.Fluctuations of vertical wind velocity _wand temperature when normalised with the respective scaling parameters u _*and _* are found to scale with Z/L in accordance with the Monin-Obukhov similarity hypothesis: % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdy2aaS% baaSqaaiaadEhaaeqaaOGaamiEaiaacIcacaWGAbGaai4laiaadYea% caGGPaWaaWbaaSqabeaacaaIXaGaai4laiaaiodaaaaaaa!3FE8!\[\phi _w x(Z/L)^{1/3} \], % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdy2aaS% baaSqaaiabeI7aXbqabaGccaWG4bGaaiikaiaadQfacaGGVaGaamit% aiaacMcadaahaaWcbeqaaiaaigdacaGGVaGaaG4maaaaaaa!40A2!\[\phi _\theta x(Z/L)^{1/3} \] during unstable conditions and % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdy2aaS% baaSqaaiaadEhaaeqaaOGaamiEaiaacIcacaWGAbGaai4laiaadYea% caGGPaaaaa!3D90!\[\phi _w x(Z/L)\], % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdy2aaS% baaSqaaiabeI7aXbqabaGccaWG4bGaaiikaiaadQfacaGGVaGaamit% aiaacMcadaahaaWcbeqaaiabgkHiTiaaigdaaaaaaa!401F!\[\phi _\theta x(Z/L)^{ - 1} \] during stable conditions. Correlation coefficients for heat and momentum flux % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeq4SdC2aaS% baaSqaaiaadEhacqaH4oqCaeqaaaaa!3A71!\[\gamma _{w\theta } \] and _uwshow stability dependence. For unstable conditions, % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeq4SdC2aaS% baaSqaaiaadEhacqaH4oqCaeqaaaaa!3A71!\[\gamma _{w\theta } \] increases with increasing ¦Z/L¦ whereas _uwdecreases. During stable conditions, % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeq4SdC2aaS% baaSqaaiaadEhacqaH4oqCaeqaaaaa!3A71!\[\gamma _{w\theta } \] decreases with increasing Z/L while _uwdecreases very slowly from a value -0.36 to -0.37.     

Hydromagnetic cylindrical shock in self-gravitating gas

Chisnell-Chester-Whitham method has been used to study the propagation of diverging hydromagnetic cylindrical shock through an infinitely electrically conducting self-gravitating gas having an initial density distribution ₀= r^-w where is the density at the axis of symmetry andw is a constant, simultaneously for the two cases, viz.: (i) when the shock is weak and (ii) when it is strong. The magnetic field is taken to be axial and initially of constant strength. Analytical relations for shock velocity and shock strength have been obtained. the expressions for the pressure, the density and the particle velocity immediately behind the shock have also been derived.     

On the Possibility of Gly and Ala Amino Acids on Titan’s Surface

In view of the possible production of formaldehyde and acetaldehyde in Titan’s atmosphere, the production of α-amino nitriles, the precursors of Glycine and Alanine amino acids, is explored in the upper atmosphere of Titan. The presence of Glycine and Alanine amino acids or their precursor amino nitriles can be used as a diagnostic, respectively for the presence or absence of water locally on the surface of Titan.     

Problems in Himalayan geology

The Central Crystalline Axis of the Great Himalaya holds clues to the solution of many problems dealing with the crystallines, metamorphics and geological contrasts encountered in the areas to the north and south of the Axis. The problems discussed include criteria for deciphering the stratigraphy in the Himalayan zone to the south of the Crystalline Axis, age of Jutogh and Chail groups, their relationship with each other and with the Crystalline Axis, nature of the Simla Slates, Jaunsar, Blaini, Infra-Krol, and Krol formations, unfossiliferous nature of the Palaeozoic and Mesozoic sediments, relationship between the Lower, Middle and Upper Tertiaries and the age, presence and absence, and also the cause of metamorphism. It has been found that high grade metamorphism is not a Tertiary phenomenon. Very low grade metamorphism in the sedimentaries and the absence of plutonic intrusives from the Palaeozoic, Mesozoic and Tertiary sedimentary rocks indicate that magmatism, regional metamorphism and orogeny are not always mutually associated in space and time. Orogenic and epeirogenic episodes other than Cretaceous-Tertiary hold clues to many problems of Himalayan Geology.

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Zusammenfassung Die zentrale kristalline Achse des Gro\en Himalaya bietet den Schlüssel für die Lösung vieler Probleme für die im Norden und Süden gelegenen Metamorphite und die geologischen GegensÄtze. Neue Daten für die Deutung der Stratigraphie in der Himalaya-Zone südlich der kristallinen Achse, das Alter der Jutogh- und der Chail-Gruppe, ihre Beziehung untereinander und zur kristallinen Achse, die Natur der Simla Slates sowie der Jaunsar-, Blaini-, Infra-Krol- und Krol-Formation, die Fossilleere der palÄozoischen und mesozoischen Sedimente, die Beziehung zwischen unterem, mittlerem und oberem TertiÄr und schlie\lich Alter, Vorkommen und Fehlen sowie die Ursache der Metamorphose werden gegeben. Hochgradige Metamorphose ist nicht an das TertiÄr gebunden. Niedriggradige Metamorphose in den Sedimenten und das Fehlen plutonischer Intrusiva aus palÄozoischen, mesozoischen und tertiÄren Sedimentgesteinen weisen darauf hin, da\ Magmatismus, regionale Metamorphose und Orogenese nicht immer zeitlich und rÄumlich miteinander verknüpft sind. Orogene und epirogene Episoden au\erhalb von Kreide und TertiÄr können wichtig für die Himalaya-Geologie sein.

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Résumé La zone axiale cristalline du Grand Himalaya apporte la clé pour la solution de nombreux problèmes concernant les métamorphites situées au Nord et au Sud, et les contrastes géologiques qu'elles présentent. De nouvelles données sont apportées sur la stratigraphie dans la zone de l'Himalaya au sud de l'axe cristallin, sur l'âge des groupes de Jutogh et de Chail, sur leurs relations mutuelles et avec l'axe cristallin, sur la nature des formations des phyllades de Simla, de Jaunsar, de Blaini, de l'Infrala nature des formations des phyllades de Simla, de Jaunsar, de Blaini, de l'Infra-Krol et de Krol, sur l'absence de fossiles dans les sédiments du PaléozoÏque et du MésozoÏque sur la présence et l'absence du métamorphisme, ainsi que sur sa cause. Le métamorphisme de degré élevé n'est pas lié au Tertiaire. Le métamorphisme de degré faible dans les sédiments et l'absence d'intrusions plutoniques dans les roches sédimentaires paléozoÏques, mésozoÏques et tertiaires montrent que le magmatisme, le métamorphisme régional et l'orogenèse ne sont pas toujours associés dans l'espace et le temps. Les épisodes orogéniques et épeirogéniques survenant en dehors du Crétacique et du Tertiaire peuvent Être importants pour la géologie himalayenne.

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. , , Jutogh Chail, , Simla Jaunsar, Blaini, Infra-Kroll & Kroll, , , , . . , , , . .

     

Semi-empirical method for calculation of maximum subsidence in coal mines

Summary Most empirical methods of subsidence prediction are based on the prior knowledge of the maximum possible subsidence, S_max, for a particular coalfield. The subsidence profile and other associated parameters along a desired line may be derived, in most cases, as a function of S _max. These methods are site specific and are not based upon the rational concepts of mechanics. Purely mechanistic methods, on the other hand, could not find wide application because of their limitations in representing the complex behaviour of a rockmass.Therefore a semi-empirical method of calculation of S _max or S, which is an improvement over the empirical method reported elsewhere (Bahuguna et al., 1991a), has been derived from combining the mechanistic and empirical approach. The effects of various parameters are studied by numerical modelling. These qualitative results are then used to influence the development of a more general semiempirical method. The method has been tested for 125 coal mine workings in India and 22 mines of the North Appalachian basin. The method is easily adaptable to other countries.     

Laser-heated diamond anvil cell experiments at high pressure: Melting curve of nickel up to 700 kbar

Laser-heated experiments in a diamond anvil cell have been performed on high pressure melting of nickel up to 700 kbar. The laser heating system consists of diamond anvil cell, Nd:YAG and argon lasers, spectrograph with diode array, computer with software, CCD camera with monitor and optics. Experiments on melting of tungsten, nickel and platinum at 1 bar outside the diamond anvil cell and melting of nickel below 80 kbar in the cell were carried out to check the system for pressure and temperature measurements. The results show that for solid pressure medium the uncertainties in measurements of pressure at the experimental spot vary between ±5 kbar at 100 kbar and ±25 kbar at 660 kbar. Spectroradiometrically determined temperature is reliable within ±70 K. Melting was detected in situ by visual observation. The melting point of nickel at 660 kbar has been found to be 2557 ±66 K.