Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Quantification of the effects of secondary matrix on the analysis of sandstone composition, and a petrographic-chemical technique for retrieving original framework grain modes of altered sandstones

Most studies of sandstone provenance involve modal analysis of framework grains using techniques that exclude the fine-grained breakdown products of labile mineral grains and rock fragments, usually termed secondary matrix or pseudomatrix. However, the data presented here demonstrate that, when the proportion of pseudomatrix in a sandstone exceeds 10%, standard petrographic analysis can lead to incorrect provenance interpretation. Petrographic schemes for provenance analysis such as QFL and QFR should not therefore be applied to sandstones containing more than 10% secondary matrix. Pseudomatrix is commonly abundant in sandstones, and this is therefore a problem for provenance analysis. The difficulty can be alleviated by the use of whole-rock chemistry in addition to petrographic analysis. Combination of chemical and point-count data permits the construction of normative compositions that approximate original framework grain compositions. Provenance analysis is also complicated in many cases by fundamental compositional alteration during weathering and transport. Many sandstones, particularly shallow marine deposits, have undergone vigorous reworking, which may destroy unstable mineral grains and rock fragments. In such cases it may not be possible to retrieve provenance information by either petrographic or chemical means. Because of this, pseudomatrix-rich sandstones should be routinely included in chemical-petrological provenance analysis. Because of the many factors, both pre- and post-depositional, that operate to increase the compositional maturity of sandstones, petrologic studies must include a complete inventory of matrix proportions, grain size and sorting parameters, and an assessment of depositional setting.     

Revised chemical models of ζ Oph based on HST data

Hubble Space Telescope observations by Savage, Cardelli and Sofia (1992) and Cardelliet al. (1993) have led to improved gas phase abundances for many elements in the diffuse cloud towards the star Oph. Most remarkably, it was found that oxygen is much more strongly depleted than previousCopernicus observations indicated. As a consequence, chemical models of the Oph cloud are severely affected by the drop in the observed oxygen abundance by almost a factor of two; some previous model calculations for the Oph cloud failed to reproduce-even approximately-the observed high CO column density. The model calculations for the Oph cloud developed by Wagenblast (1992) in which the abundance of all observed neutral molecules could be reproduced have been revised and it is found that oxygen and nitrogen hydrides are required to be formed efficiently on the surface of grains; further, there are indications for a high cosmic ray ionization rate of the order 10^–16 s^–1.     

The GEM project: An international collaboration to survey galactic radiation emission

The GEM (Galactic Emission Mapping) project is an international collaboration established with the aim of surveying the full sky at long wavelengths with a multi-frequency radio telescope. A total of 745 hours of observation at 408 MHz were completed from an Equatorial site in Colombia. The observations cover the celestial band 0 ^h <<24 ^h , and –24° 22<<+35° 37. Preliminary results of this partial survey will be discussed. A review of the instrumental setup and a 10° resolution sky map at 408 MHz is presented.Presented by S. Torres at the UN/ESA Workshop on Basic Space Sciences: From Small Telescopes to Space Missions, Colombo, Sri Lanka 11–14 January 1996     

Propagation of solar cosmic rays: Diffusion versus focused diffusion

This paper is designed to bring to the attention the fact that the effect of focusing of solar energetic particles is always essential as compared with scattering, no matter how small the value of the mean free path may be. That is why, an ordinary (focusing-free) diffusion approach can not be applied to the solar cosmic ray transport. In the case of high-energy solar particles, the focused diffusion is demonstrated to lead to a power law decay of energetic particle intensity much like an ordinary diffusion. However, the power law index of the decay is renormalized by the focusing.     

Whistler observations of the quiet time plasmasphere-ionosphere coupling fluxes at low latitude

Observations of whistlers during quiet times made at low-latitude ground station Nainital (geomag. lat. 19 1 N) are used to deduce plasmasphere-ionosphere coupling fluxes. The whistler data from 3 magnetically quiet days are presented that show a smooth decrease in dispersion with time. This decrease in dispersion is interpreted in terms of a corresponding decrease in electron content of tubes of ionization. The electron densities, electron tube contents (10¹⁶ el/m²-tube) and coupling fluxes (10 el m^–1 s^–2) are computed by means of an accurate curve fitting method developed by Tarcsai (1975) and are in good agreement with the results reported by other workers.     

Coherent eddies and turbulence in vegetation canopies: The mixing-layer analogy

This paper argues that the active turbulence and coherent motions near the top of a vegetation canopy are patterned on a plane mixing layer, because of instabilities associated with the characteristic strong inflection in the mean velocity profile. Mixing-layer turbulence, formed around the inflectional mean velocity profile which develops between two coflowing streams of different velocities, differs in several ways from turbulence in a surface layer. Through these differences, the mixing-layer analogy provides an explanation for many of the observed distinctive features of canopy turbulence. These include: (a) ratios between components of the Reynolds stress tensor; (b) the ratio K _H/K _M of the eddy diffusivities for heat and momentum; (c) the relative roles of ejections and sweeps; (d) the behaviour of the turbulent energy balance, particularly the major role of turbulent transport; and (e) the behaviour of the turbulent length scales of the active coherent motions (the dominant eddies responsible for vertical transfer near the top of the canopy). It is predicted that these length scales are controlled by the shear length scale % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamitamaaBa% aaleaacaWGtbaabeaakiabg2da9iaadwfacaGGOaGaamiAaiaacMca% caGGVaGabmyvayaafaGaaiikaiaadIgacaGGPaaaaa!3FD0!\[L_S = U(h)/U'(h)\] (where h is canopy height, U(z) is mean velocity as a function of height z, and % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGabmyvayaafa% Gaeyypa0JaaeizaiaadwfacaGGVaGaaeizaiaadQhaaaa!3C32!\[U' = {\rm{d}}U/{\rm{d}}z\]). In particular, the streamwise spacing of the dominant canopy eddies is _x = mL _s, with m = 8.1. These predictions are tested against many sets of field and wind-tunnel data. We propose a picture of canopy turbulence in which eddies associated with inflectional instabilities are modulated by larger-scale, inactive turbulence, which is quasi-horizontal on the scale of the canopy.     

A wind tunnel study of turbulent flow around single and multiple windbreaks, part I: Velocity fields

This paper describes wind-tunnel experiments on the flow around single and multiple porous windbreaks (height H), sheltering a model plant canopy (height H/3). The mean wind is normal to the windbreaks, which span the width of the wind tunnel. The incident turbulent flow simulates the adiabatic atmospheric surface layer. Five configurations are examined: single breaks of three solidities (low, medium, high; solidity = 1 - porosity), and medium-solidity multiple breaks of streamwise spacing 12H and 6H. The experimental emphases are on the interactions of the windbreak flow with the underlying plant canopy; the effects of solidity; the differences in shelter between single and multiple windbreaks; and the scaling properties of the flow. Principal results are: (1) the "quiet zones" behind each windbreak are smaller in multiple than single arrays, because of the higher turbulence level in the very rough-wall internal boundary layer which develops over the multiple arrays. Nevertheless, the overall shelter effectiveness is higher for multiple arrays than single windbreaks because of the "nonlocal shelter" induced by the array as a whole. (2) The flow approaching the windbreak decelerates above the canopy but accelerates within the canopy, particularly when the windbreak solidity is high. (3) A strong mixing layer forms just downwind of the top of each windbreak, showing some of the turbulence and scaling properties of the classical mixing layer formed between uniform, coflowing streams. (4) No dramatic increase in turbulence levels in the canopy is evident at the point where the deepening mixing layer contacts the canopy (around x/H = 3) but the characteristic inflection in the canopy wind profile is eliminated at this point.     

Surface renewal analysis for sensible and latent heat flux density

High frequency temperature measurements were recorded at five heights and surface renewal (SR) analysis was used to estimate sensible heat flux density (H) over 0.1 m tall grass. Traces of the temperature data showed ramp-like structures, and the mean amplitude and duration of these ramps were used to calculate H using structure functions. Data were compared with H values measured with a sonic anemometer. Latent heat flux density (E) was calculated using an energy balance and the results were compared with E computed from the sonic anemometer data. SR analysis provided good estimates of H for data recorded at all heights but the canopy top and at the highest measurement level, which was above the fully adjusted boundary layer.     

Climate change and snow-cover duration in the Australian Alps

This study uses a model of snow-cover duration, an observed climate data set for the Australian alpine area, and a set of regional climate-change scenarios to assess quantitatively how changes in climate may affect snow cover in the Australian Alps. To begin, a regional interannual climate data set of high spatial resolution is prepared for input to the snow model and the resulting simulated interannual and spatial variations in snow-cover duration are assessed and compared with observations. The model provides a reasonable simulation of the sensitivities of snow-cover duration to changes in temperature and precipitation in the Australian Alps, although its performance is poorer at sites highly marginal for snow cover. (In a separate comparison, the model also performs well for sites in the European Alps.) The input climate data are then modified in line with scenarios of regional climate change based on the results of five global climate models run in enhanced greenhouse experiments. The scenarios are for the years 2030 and 2070 and allow for uncertainty associated with projecting future emissions of greenhouse gases and with estimating the sensitivity of the global climate system to enhanced greenhouse forcing. Attention focuses on the climate changes most favourable (best-case scenario) and least favourable (worst-case scenario) for snow cover amongst the range of climate changes in the scenarios. Under the best case scenario for 2030, simulated average snow-cover duration and the frequency of years of more than 60 days cover decline at all sites considered. However, at the higher sites (e.g., more than 1700 m) the effect is not very marked. For the worst case scenario, a much more dramatic decline in snow conditions is simulated. At higher sites, simulated average snow cover duration roughly halves by 2030 and approaches zero by 2070. At lower sites (around 1400 m), near zero average values are simulated by 2030 (compared to durations of around 60 days for current climate).These simulated changes, ranging between the best and worst case, are likely to be indicative of how climate change will affect natural snow-cover duration in the Australian Alps. However, note that the model does not allow directly for changes in the frequency and intensity of snow-bearing circulation systems, nor do the climate-change scenarios allow possible changes in interannual variability (particularly that due to the El Niño-Southern Oscillation) and local topographical effects not resolved by global climate models. The simulated changes in snow cover are worthy of further consideration in terms of their implications for the ski industry and tourism, water resources and hydroelectric power, and land-use management and planning.68 Barada Crescent, Aranda ACT 2614, Australia.