Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O₂ of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with O₂ versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, (H)=(H_{decomposition}–H_{O 2 reaction}), between these two reactions pathways. For (H)[22–0.5(H_{O 2 reaction})], alkoxy radical decomposition dominates over the reaction with O₂ at room temperature and atmospheric pressure of air, while for (H)[25-0.5(H_{O 2 reaction})], the O₂ reaction dominates over decomposition (where the units of H are in kcal mol^–1). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed.     

Nd,Sr, and O isotopic variations in metaluminous ash-flow tuffs and related volcanic rocks at the Timber Mountain/Oasis Valley Caldera,Complex, SW Nevada: implications for the origin and evolution of large-volume silicic magma bodies

Nd, Sr and O isotopic data were obtained from silicic ash-flow tuffs and lavas at the Tertiary age (16–9 Ma) Timber (Mountain/Oasis Valley volcanic center (TMOV) in southern Nevada, to assess models for the origin and evolution of the large-volume silicic magma bodies generated in this region. The large-volume (>900 km³), chemically-zoned, Topopah Spring (TS) and Tiva Canyon (TC) members of the Paintbrush Tuff, and the Rainier Mesa (RM) and Ammonia Tanks (AT) members of the younger Timber Mountain Tuff all have internal Nd and Sr isotopic zonations. In each tuff, high-silica rhyolites have lower initial _Nd values (1 _Nd unit), higher⁸⁷Sr/⁸⁶Sr, and lower Nd and Sr contents, than cocrupted trachytes. The TS, TC, and RM members have similar _Nd values for high-silica rhyolites (-11.7 to -11.2) and trachytes (-10.5 to -10.7), but the younger AT member has a higher _Nd for both compositional types (-10.3 and -9.4). Oxygen isotope data confirm that the TC and AT members were derived from low _Nd magmas. The internal Sr and Nd isotopic variations in each tuff are interpreted to be the result of the incorporation of 20–40% (by mass) wall-rock into magmas that were injected into the upper crust. The low _Nd magmas most likely formed via the incorporation of low ¹⁸O, hydrothermally-altered, wall-rock. Small-volume rhyolite lavas and ash-flow tuffs have similar isotopic characteristics to the large-volume ash-flow tuffs, but lavas erupted from extracaldera vents may have interacted with higher ¹⁸O crustal rocks peripheral to the main magma chamber(s). Andesitic lavas from the 13–14 Ma Wahmonie/Salyer volcanic center southeast of the TMOV have low _Nd (-13.2 to -13.8) and are considered on the basis of textural evidence to be mixtures of basaltic composition magmas and large proportions (70–80%) of anatectic crustal melts. A similar process may have occurred early in the magmatic history of the TMOV. The large-volume rhyolites may represent a mature stage of magmatism after repeated injection of basaltic magmas, crustal melting, and volcanism cleared sufficient space in the upper crust for large magma bodies to accumulate and differentiate. The TMOV rhyolites and 0–10 Ma old basalts that erupted in southern Nevada all have similar Nd and Sr isotopic compositions, which suggests that silicic and mafic magmatism at the TMOV were genetically related. The distinctive isotopic compositions of the AT member may reflect temporal changes in the isotopic compositions of basaltic magmas entering the upper crust, possibly as a result of increasing basification of a lower crustal magma source by repeated injection of mantle-derived mafic magmas.     

The evolution and orientation of early cycle 22 active regions

The evolution of six major active regions which appeared during the first phase of the present solar cycle (cycle 22) has been studied. It was found that the northern hemisphere regions exhibited a broad range of evolutionary behavior in which the commonly accepted normal pattern (whereby the follower flux moves preferentially polewards ahead of the leader flux) is represented only at one end of the range. At the other end of the range, the leader flux is displaced polewards of the follower flux. In the latter cases equatorward extensions of the polar coronal hole are noted.While it is emphasized that some of the regions in this study follow the more conventional pattern and that all regions in this study emerged during the early phase of cycle 22, the implications for theories of the solar polar field reversals are noted.     

Exports and Growth: Learning from the Case of Southern U.S. Metropolitan Areas

The relationship between exports and economic growth is a paradigmatic element of modern economic growth policy, despite the absence of strong evidence of a connection. Until recently, data on export production prevented an extensive empirical analysis of metropolitan-scale trade. This article examines the export growth dynamics across large metropolitan statistical areas (MSAs) within the southern United States, a region that has been impacted by economic globalization. These analyses found that some Southern metropolitan areas differ from regional and national averages in selected measures of export performance. Additionally, the export performance of Southern cities was not correlated with all indicators of economic development. This article concludes that export dynamics should be viewed increasingly from an urban frame, with particular emphasis on the production of globally consumed knowledge products and advanced manufacturing. Moreover, export policy should be directed toward the individual strengths of urban regions.     

The nonlinear spin-up of a stratified ocean

Abstract

The adjustment of a nonlinear, quasigeostrophic, stratified ocean to an impulsively applied wind stress is investigated under the assumption that barotropic advection of vortex tube length is the most important nonlinearity. The present study complements the steady state theories which have recently appeared, and extends earlier, dissipationless, linear models.

In terms of Sverdrup transport, the equation for baroclinic evolution is a forced advection-diffusion equation. Solutions of this equation subject to a “tilted disk” Ekman divergence are obtained analytically for the case of no diffusion and numerically otherwise. The similarity between the present equation and that of a forced barotropic fluid with bottom topography is shown.

Barotropic flow, which is assumed to mature instantly, can reverse the tendency for westward propagation, and thus produce regions of closed geostrophic contours. Inside these regions, dissipation, or equivalently the eddy field, plays a central role. We assume that eddy mixing effects a lateral, down-gradient diffusion of potential vorticity; hence, within the closed geostrophic contours, our model approaches a state of uniform potential vorticity. The solutions also extend the steady-state theories, which require weak diffusion, by demonstrating that homogenization occurs for moderately strong diffusion.

The evoiution of potential vorticity and the thermocline are examined, and it is shown that the adjustment time of the model is governed by dissipation, rather than baroclinic wave propagation as in linear theories. If dissipation is weak, spin-up of a nonlinear ocean may take several times that predicted by linear models, which agrees with analyses of eddy-resolving general circulation models. The inclusion of a western boundary current may accelerate this process, although dissipation will still play a central role.     

Open-ocean response and normal mode excitation in an eddy-resolving general circulation model

Abstract

Analysis of a two-layer, flat-bottom, steady-wind driven, eddy-resolving general circulation model reveals a distinct separation in frequency of baroclinic and barotropic motion in the region distant from the model Gulf Stream. The far-field motions at periods less (greater) than about 100 days are predominantly barotropic (baroclinic), unlike the near-field, eddy-generating, free-jet region which contains barotropic and baroclinic energy throughout the modei frequency range. The far-field barotropic energy produces a peak in the model sea-level spectra between 25 and 50 days with a magnitude comparable to energy levels observed in spectra of sea level from oceanic island tide gauges. The far-field barotropic motion is clearly composed of large-scale, resonant, barotropic normal modes drive by mesoscale activity of the turbulent, free-jet region. Oceanic mesoscale turbulence may therefore provide for planetary normal modes an excitation mechanism distinct from atmospheric forcing. The open-ocean, barotropic, model response is very similar to that of a fluctuating-wind driven model, which suggests that atmospheric and intrinsic forcing of mid-ocean eddies may be of comparable importance.     

Energy spectra associated with long's model for steady finite-amplitude flow over orography

Abstract

The process of wave steepening in Long's model of steady, two-dimensional stably stratified flow over orography is examined. Under conditions of the long-wave approximation, and constant values of the background static stability and basic flow, Long's equation is cast into the form of a nonlinear advection equation. Spectral properties of this latter equation, which could be useful for the interpretation of data analyses under mountain wave conditions, are presented. The principal features, that apply at the onset of convective instability (density constant with height), are:

i) a power spectrum for available potential energy that exhibits a minus eight-thirds decay, in terms of the vertical wavenumber k _z ^-;

ii) a rate of energy transfer across the spectrum that is inversely proportional to the wavenumber for large k _z ^-;

iii) an equipartition between the kinetic energy of the horizontal motion and the available potential energy, under the longwave approximation, although all the disturbance energy is kinetic at the point where convective instability is initiated. It is also shown that features i) and ii) apply to more general conditions that are appropriate to Long's model, not just the long-wave approximation. Application to fully turbulent flow or to conditions at the onset of shearing instability are not considered to be warranted, since the development only applies to conditions at the onset of convective instability.