A study of thermal decompositions of an allylic hydroperoxide /|nby Thomas A. McCarrick. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

The thermal decomposition of 2,3-di~ethy l - J-hydr operox y- 1 - butene , p r epared f rol") singl e t oxygen, has been studied i n three solvents over the tempe r a ture r ange from 1500e to l o00e and t!1e i 111 t ial ~oncentrfttl nn r Ange from O. 01 M to 0.2 M. Analys i s of the kine tic data ind ica te s i nduced homolysis as the n ost probRble mode of d e composition, g iving rise to a 3/2 f S order dependence upon hy d.roperoxide concent :r8.tl on . Experimental activation e nergies for the decomposition were f ound to be between 29.5 kcsl./raole and 30.0 k cal./mole .• \,iith log A factors between 11 . 3 and 12.3. Product studies were conducted in R variety of solvents a s well as in the pr esence of a variety of free r adical initiators . Investigation of the kinetic ch a in length indicated a chain length of about fifty. A degenerat i ve chain branching mechanism 1s proposed which predicts the multi t ude of products which Rre observed e xperimentally as well as giving activation energies and log A factors si~il a r to those found experimentally .

Unusually high differential attenuation at C band: Results from a two-year analysis of the French Trappes polarimetric radar data

The differential phase (ΦDP) measured by polarimetric radars is recognized to be a very good indicator of the path integrated by rain. Moreover, if a linear relationship is assumed between the specific differential phase (KDP) and the specific attenuation (AH) and specific differential attenuation (ADP), then attenuation can easily be corrected. The coefficients of proportionality, γH and γDP, are, however, known to be dependent in rain upon drop temperature, drop shapes, drop size distribution, and the presence of large drops causing Mie scattering. In this paper, the authors extensively apply a physically based method, often referred to as the “Smyth and Illingworth constraint,” which uses the constraint that the value of the differential reflectivity ZDR on the far side of the storm should be low to retrieve the γDP coefficient. More than 30 convective episodes observed by the French operational C-band polarimetric Trappes radar during two summers (2005 and 2006) are used to document the variability of γDP with respect to the intrinsic three-dimensional characteristics of the attenuating cells. The Smyth and Illingworth constraint could be applied to only 20% of all attenuated rays of the 2-yr dataset so it cannot be considered the unique solution for attenuation correction in an operational setting but is useful for characterizing the properties of the strongly attenuating cells. The range of variation of γDP is shown to be extremely large, with minimal, maximal, and mean values being, respectively, equal to 0.01, 0.11, and 0.025 dB °−1. Coefficient γDP appears to be almost linearly correlated with the horizontal reflectivity (ZH), differential reflectivity (ZDR), and specific differential phase (KDP) and correlation coefficient (ρHV) of the attenuating cells. The temperature effect is negligible with respect to that of the microphysical properties of the attenuating cells. Unusually large values of γDP, above 0.06 dB °−1, often referred to as “hot spots,” are reported for 15%—a nonnegligible figure—of the rays presenting a significant total differential phase shift (ΔϕDP > 30°). The corresponding strongly attenuating cells are shown to have extremely high ZDR (above 4 dB) and ZH (above 55 dBZ), very low ρHV (below 0.94), and high KDP (above 4° km−1). Analysis of 4 yr of observed raindrop spectra does not reproduce such low values of ρHV, suggesting that (wet) ice is likely to be present in the precipitation medium and responsible for the attenuation and high phase shifts. Furthermore, if melting ice is responsible for the high phase shifts, this suggests that KDP may not be uniquely related to rainfall rate but can result from the presence of wet ice. This hypothesis is supported by the analysis of the vertical profiles of horizontal reflectivity and the values of conventional probability of hail indexes.

Evaluation of two "integrated" polarimetric Quantitative Precipitation Estimation (QPE) algorithms at C-band

Two so-called “integrated” polarimetric rate estimation techniques, ZPHI (Testud et al., 2000) and ZZDR (Illingworth and Thompson, 2005), are evaluated using 12 episodes of the year 2005 observed by the French C-band operational Trappes radar, located near Paris. The term “integrated” means that the concentration parameter of the drop size distribution is assumed to be constant over some area and the algorithms retrieve it using the polarimetric variables in that area. The evaluation is carried out in ideal conditions (no partial beam blocking, no ground-clutter contamination, no bright band contamination, a posteriori calibration of the radar variables ZH and ZDR) using hourly rain gauges located at distances less than 60 km from the radar. Also included in the comparison, for the sake of benchmarking, is a conventional Z = 282R1.66 estimator, with and without attenuation correction and with and without adjustment by rain gauges as currently done operationally at Météo France. Under those ideal conditions, the two polarimetric algorithms, which rely solely on radar data, appear to perform as well if not better, pending on the measurements conditions (attenuation, rain rates, …), than the conventional algorithms, even when the latter take into account rain gauges through the adjustment scheme. ZZDR with attenuation correction is the best estimator for hourly rain gauge accumulations lower than 5 mm h−1 and ZPHI is the best one above that threshold. A perturbation analysis has been conducted to assess the sensitivity of the various estimators with respect to biases on ZH and ZDR, taking into account the typical accuracy and stability that can be reasonably achieved with modern operational radars these days (1 dB on ZH and 0.2 dB on ZDR). A +1 dB positive bias on ZH (radar too hot) results in a +14% overestimation of the rain rate with the conventional estimator used in this study (Z = 282R^1.66), a -19% underestimation with ZPHI and a +23% overestimation with ZZDR. Additionally, a +0.2 dB positive bias on ZDR results in a typical rain rate under- estimation of 15% by ZZDR.

Particle acceleration and magnetic field structure in PKS 2155-304: optical polarimetric observations

In this paper, we present multiband optical polarimetric observations of the very-high energy blazar PKS 2155-304 made simultaneously with a HESS/Fermi high-energy campaign in 2008, when the source was found to be in a low state. The intense daily coverage of the data set allowed us to study in detail the temporal evolution of the emission, and we found that the particle acceleration time-scales are decoupled from the changes in the polarimetric properties of the source. We present a model in which the optical polarimetric emission originates at the polarized mm-wave core and propose an explanation for the lack of correlation between the photometric and polarimetric fluxes. The optical emission is consistent with an inhomogeneous synchrotron source in which the large-scale field is locally organized by a shock in which particle acceleration takes place. Finally, we use these optical polarimetric observations of PKS 2155-304 at a low state to propose an origin for the quiescent gamma-ray flux of the object, in an attempt to provide clues for the source of its recently established persistent TeV emission.

Mapping Macrophyte Species in the Amazon Floodplain Wetlands Using Fully Polarimetric ALOS/PALSAR Data

The purpose of this paper was to evaluate attributes derived from fully polarimetric PALSAR data to discriminate and map macrophyte species in the Amazon floodplain wetlands. Fieldwork was carried out almost simultaneously to the radar acquisition, and macrophyte biomass and morphological variables were measured in the field. Attributes were calculated from the covariance matrix [C] derived from the single-look complex data. Image attributes and macrophyte variables were compared and analyzed to investigate the sensitivity of the attributes for discriminating among species. Based on these analyses, a rule-based classification was applied to map macrophyte species. Other classification approaches were tested and compared to the rule-based method: a classification based on the Freeman-Durden and Cloude-Pottier decomposition models, a hybrid classification (Wishart classifier with the input classes based on the H/a plane), and a statistical-based classification (supervised classification using Wishart distance measures). The findings show that attributes derived from fully polarimetric L-band data have good potential for discriminating herbaceous plant species based on morphology and that estimation of plant biomass and productivity could be improved by using these polarimetric attributes.

Dynamic Morse decompositions for semigroups of homeomorphisms and control systems

In this paper, we introduce the concept of dynamic Morse decomposition for an action of a semigroup of homeomorphisms. Conley has shown in [5, Sec. 7] that the concepts of Morse decomposition and dynamic Morse decompositions are equivalent for flows in metric spaces. Here, we show that a Morse decomposition for an action of a semigroup of homeomorphisms of a compact topological space is a dynamic Morse decomposition. We also define Morse decompositions and dynamic Morse decompositions for control systems on manifolds. Under certain condition, we show that the concept of dynamic Morse decomposition for control system is equivalent to the concept of Morse decomposition.

Critical evaluation of FBD, pq and CPT current decompositions for four-wire circuits

This paper investigates the major similarities and discrepancies of three important current decompositions proposed for the interpretation of unbalanced and/or non linear three-phase four-wire circuits. The considered approaches were the so-called FBD Theory, the pq-Theory and the CPT. Although the methods are based on different concepts, the results obtained under ideal conditions (sinusoidal and balanced signals) are very similar. The main differences appear in the presence of unbalanced and non linear load conditions. It will be demonstrated and discussed how the choice of the voltage referential and the return conductor impedance can influence in the resulting current components, as well as, the way of interpreting a power circuit with return conductor. Under linear unbalanced conditions, both FBD and pq-Theory suggest that the some current components contain a third-order harmonic. Besides, neither pq-Theory nor FBD method are able to provide accurate information for reactive current under unbalanced and distorted conditions, what seems to be done by means of the CPT. © 2009 IEEE.

A comparative analysis of FBD, PQ and CPT current decompositions - Part II: Three-phase four-wire systems

This paper investigates the major similarities and discrepancies among three important current decompositions proposed for the interpretation of unbalanced and/or non linear three-phase four-wire power circuits. The considered approaches were the so-called FBD Theory, the pq-Theory and the CPT. Although the methods are based on different concepts, the results obtained under ideal conditions (sinusoidal and balanced signals) are very similar. The main differences appear in the presence of unbalanced and non linear load conditions. It will be demonstrated and discussed how the choice of the voltage referential and the return conductor impedance can influence in the resulting current components, as well as, the way of interpreting a power circuit with return conductor. Under linear unbalanced conditions, both FBD and pq-Theory suggest that the some current components contain a third-order harmonic. Besides, neither pq-Theory nor FBD method are able to provide accurate information for reactive current under unbalanced and distorted conditions, what can be done by means of the CPT. © 2009 IEEE.

Investigations on the full polarimetric PALSAR data to discriminate macrophytes species in the Amazon floodplain wetland

The purpose of this work is to evaluate the capacity of full polarimetric L band data to discriminate macrophyte species in Amazon wetland. Fieldwork was carried out almost simultaneously to the acquisition of the full polarimetric PALSAR data. Coherent and incoherent attributes were extracted from the image, and macrophyte morphological variables were measured on the ground. The image attributes and the macrophyte variables were compared in order to evaluate their application for discriminating macrophytes species. The findings suggest that polarimetric information could be adopted to discriminate plant species based on morphology, and that estimation of plant biomass and productivity could be improved by using the polarimetric information. © 2010 IEEE.

Avaliação do potencial de dados polarimétricos Radarsat-2 para mapeamento de uso e cobertura da terra em trecho de faixa de dutos sobre diferentes condições geomorfológicas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Polarimetric X-band weather radar measurements in the tropics: radome and rain attenuation correction

A polarimetric X-band radar has been deployed during one month (April 2011) for a field campaign in Fortaleza, Brazil, together with three additional laser disdrometers. The disdrometers are capable of measuring the raindrop size distributions (DSDs), hence making it possible to forward-model theoretical polarimetric X-band radar observables at the point where the instruments are located. This setup allows to thoroughly test the accuracy of the X-band radar measurements as well as the algorithms that are used to correct the radar data for radome and rain attenuation. For the campaign in Fortaleza it was found that radome attenuation dominantly affects the measurements. With an algorithm that is based on the self-consistency of the polarimetric observables, the radome induced reflectivity offset was estimated. Offset corrected measurements were then further corrected for rain attenuation with two different schemes. The performance of the post-processing steps was analyzed by comparing the data with disdrometer-inferred polarimetric variables that were measured at a distance of 20 km from the radar. Radome attenuation reached values up to 14 dB which was found to be consistent with an empirical radome attenuation vs. rain intensity relation that was previously developed for the same radar type. In contrast to previous work, our results suggest that radome attenuation should be estimated individually for every view direction of the radar in order to obtain homogenous reflectivity fields.