Dinámica y cinética de los procesos físicos y químicos del radical OH con compuestos orgánicos volátiles (COVs) de relevancia atmosférica. Dynamics and kinetics of the physical and chemical processes of OH radicals with atmospheric relevant volatile organic compounds (VOCs)

El objetivo del presente proyecto es estudiar los procesos físicos y químicos del radical OH con compuestos orgánicos volátiles (COVs), con los cuales sea factible la formación de agregados de van der Waals (vdW) responsables de la curvatura en los gráficos de Arrhenius, empleando técnicas modernas, complementarias entre si y novedosas en el país. El problema será abordado desde tres perspectivas complementarias: 1) estudios cinéticos, 2) estudios mecanísticos y de distribución de productos y 3) estudios de la dinámica de los procesos físicos y químicos. La finalidad es alcanzar una mejor comprensión de los mecanismos que intervienen en el comportamiento químico de especies presentes en la atmósfera y obtener datos cinéticos de alta calidad que puedan alimentar modelos computacionales capaces de describir la composición de la atmósfera, presente y futura. Los objetivos son estudiar: 1) mediante fotólisis láser pulsada con detección por fluorescencia inducida por láser (PLP-LIF), en reactores de flujo, la cinética de reacción del radical OH(v”=0) con COVs que presentan gráficos de Arrhenius curvos con energías de activación negativas, tales como alcoholes insaturados, alquenos halogenados, éteres halogenados, ésteres alifáticos; 2) en una cámara de simulación de condiciones atmosféricas de gran volumen (4500 L), la identidad y el rendimiento de productos de las reacciones mencionadas, a fines de evaluar su impacto atmosférico y dilucidar los mecanismos de reacción; 3) mediante haces moleculares y espectroscopía láser, la estructura y reactividad de complejos de vdW entre alcoholes insaturados o aromáticos (cresoles) y el radical OH, como modelo de los aductos propuestos como responsables de la desviación al comportamiento de Arrhenius de las reacciones mencionadas; 4) mediante PLP-LIF y expansiones supersónicas, las constantes específicas estado a estado (ksts) de relajación/reacción del radical OH(v”=1-4) vibracionalmente excitado con los COVs mencionados. Los resultados experimentales obtenidos serán contrastados con cálculos ab-initio de estructura electrónica, los cuales apoyarán las interpretaciones, permitirán proponer estructuras de estados de transición y aductos colisionales, como así también calcular las frecuencias de vibración de los complejos de vdW para su posterior asignación en los espectros LIF y REMPI. Asimismo, los mecanismos de reacción propuestos y los parámetros cinéticos medidos experimentalmente serán comparados con aquellos obtenidos por cálculos teóricos. The aim of this project is to study the physical and chemical processes of OH radicals with volatile organic compounds (VOCs) with which the formation of van der Waals (vdW) clusters, responsible for the observed curvature in the Arrhenius plots, might be feasible. The problem will be addressed as follow : 1) kinetic studies; 2) products distribution and mechanistic studies and 3) dynamical studies of the physical and chemical processes. The purpose is to obtain a better understanding of the mechanisms that govern the chemical behavior of species present in the atmosphere and to obtain high quality kinetic data to be used as input to computational models. We will study: 1) the reaction kinetics of OH (v”=0) radicals with VOCs such as unsaturated alcohols, halogenated alkenes, halogenated ethers, aliphatic esters, which show curved Arrhenius plots and negative activation energies, by PLP-LIF, in flow systems; 2) in a large volume (4500 L) atmospheric simulation chamber, reaction products yields in order to evaluate their atmospheric impact and reaction mechanisms; 3) using molecular beams and laser spectroscopy, the structure and reactivity of the vdW complexes formed between the unsaturated or aromatic alcohols and the OH radicals as a model of the adducts proposed as responsible for the non-Arrhenius behavior; 4) the specific state-to-state relaxation/reaction rate constants (ksts) of the vibrationally excited OH (v”=1-4) radical with the VOCs by PLP-LIF and supersonic expansions. Ab-initio calculations will be carried out to support the interpretation of the experimental results, to obtain the transition state and collisional adducts structures, as well as to calculate the vibrational frequencies of the vdW complexes to assign to the LIF and REMPI spectra. Also, the proposed reaction mechanisms and the experimentally measured kinetic parameters will be compared with those obtained from theoretical calculations.

Ireland's biodegradable municipal waste

This project focuses on the EU Landfill Directive targets for Biodegradable Municipal Waste (BMW) specifically focusing on how the targets will affect Ireland and its waste management infrastructure. Research will consist of reviewing relevant literature, legislation and policies that will provide a comparable between Ireland and other nations. Planning processes which govern both the building structure and running capacities of treatment facilities is also necessary in order to predict amounts of waste diverted from landfill. The efficiency of these treatment plants also requires investigation. Another objective is to research further information on Irelands organic ‘brown’ bin service, this will involve discovering the roll out of bins in the future over a defined time scale as well as the potential amounts of waste that will be collected. Figures received from waste management and waste treatment companies will be combined with figures from the Environmental Protection Agency’s (EPA) annual reports. This will give an indication to past trends and shed light on possible future trends. With this information annul waste volumes consigned to landfill can be calculated and used to determine whether or not Ireland can achieve the EU Landfill Directive targets. Without significant investment in Irelands waste management infrastructure it is unlikely that the targets will be met. Existing waste treatment facilities need to be managed as efficiently as possible. Waste streams must also be managed so waste is shared appropriately between companies and not create a monopolising waste treatment facility. The driving forces behind an efficient waste management infrastructure are government policy and legislation. An overall and efficient waste management strategy must be in place, along with disincentives for landfilling of waste such as the landfill levy. Encouragement and education of the population is the fundamental and first step to achieving the landfill directive targets.

Data for the sustainable management of an emerging fishery: Age, growth and stock structure of Atlantic saury Scomberesox saurus saurus (Walbaum), in the Northeastern Atlantic Ocean

Almost half of Ireland’s commercial stocks face overexploitation. As traditional species decrease in abundance and become less profitable, the industry is increasingly turning to alternate species. Atlantic saury (Scomberesox saurus saurus (Walbaum)) has been identified as a potential species for exploitation. Very little information is available on its biology or population dynamics, especially for Irish waters. This thesis aims to obtain sound scientific data, which will help to ensure that a future Atlantic saury fishery can be sustainably managed. The research has produced valuable data, some of which contradicts previous studies. Growth of Atlantic saury measured using otolith microstructure is found to be more than twice that previously calculated from annual structures on scales and otoliths. This results in a significant reduction of the expected life span from five to about two years. Investigation of maturity stage at age indicates that Atlantic saury will reproduce for the first time at age one and will survive for one or at most two reproduction seasons. It is concluded that a future Irish fishery will target mostly fish prior to their first reproduction. Finally the thesis gives some insights into the population structure of Atlantic saury, by analysis of otolith morphometric. Significant differences are detected between Northeastern Atlantic and western Mediterranean Sea specimens of the 0+ age class (less than one year old). The implications of these results for the management of an emerging fishery are discussed.

Escore de cálcio para avaliar dor torácica na sala de emergência

Alguns autores têm sugerido que um escore de cálcio (CAC) igual à zero pode ser usado para descartar o diagnóstico de síndrome coronariana aguda. Objetivo do estudo é avaliar a precisão do diagnóstico de um CAC zero quando comparado com a angiotomografia coronária (ATC) no Pronto-Socorro. 135 pacientes sintomáticos sem doença arterial coronariana (DAC) prévia atendidos no Pronto-Socorro, foram submetidos ao CAC e à ATC para descartar a DAC. Todos os pacientes tinham eletrocardiograma e marcadores cardíacos normais e apresentaram escore de risco TIMI de 0 a 2. A ATC foi considerada positiva no caso de identificação de qualquer lesão obstrutiva (> 50%). A média de idade era de 51,7 ± 13,6 anos, com 50,6% de homens. Setenta e três (54,1%) pacientes apresentaram um escore zero de cálcio. Desses, 3 (4,1%) tiveram uma obstrução > 50% e foram submetidos a angiografia coronária invasiva. O escore de cálcio mostrou uma sensibilidade de 92,9%, especificidade de 75,3% e valores preditivos positivos e negativos de, respectivamente, 62,9% e 95,9%. As razões de verossimilhança positiva e negativa foram respectivamente de 3,7 e 0,09 para a detecção de lesões maiores do que 50% na ATC. A razão de verossimilhança negativa de 0,09 é muito boa para descartar a maioria dos casos de obstrução coronária significativa em estudos epidemiológicos. No entanto, é importante entender que em um cenário clínico, todas as evidências, incluindo histórico, exame clínico, dados de biomarcadores miocárdicos e do eletrocardiograma, devem ser interpretados em conjunto. Em nosso estudo, três casos com um escore CAC zero tinham obstrução coronariana superior a 50% na ATC.

Espessura do tecido subcutaneo como preditor independente de ruido em imagem de TC cardiaca

Fundamento: Há poucos dados sobre a definição de parâmetros simples e robustos para predizer artefato de imagem em tomografia computadorizada (TC) cardíaca. Objetivos: Avaliar o valor da simples medida da espessura do tecido subcutâneo (espessura pele-esterno) como preditor de artefato de imagem em TC cardíaca. Métodos: O estudo avaliou 86 pacientes submetidos a angiotomografia computadorizada cardíaca (ATCC) com sincronização prospectiva com ECG e avaliação de escore de cálcio coronário com 120 kV e 150 mA. A qualidade da imagem foi medida objetivamente pelo artefato de imagem na aorta em ATCC, sendo 'artefato baixo' definido como aquele < 30 UH. Os diâmetros torácicos anteroposterior e laterolateral, o artefato de imagem na aorta e a espessura pele-esterno foram medidos como preditores de artefato em ATCC. A associação de preditores e artefato de imagem foi avaliada usando-se correlação de Pearson. Resultados: A dose média de radiação foi 3,5 ± 1,5 mSv. O artefato de imagem médio na ATCC foi de 36,3 ± 8,5 UH, sendo o artefato de imagem médiona fase sem contraste do exame de 17,7 ± 4,4 UH. Todos os preditores foram independentemente associados com artefato em ATCC. Os melhores preditores foram espessura pele-esterno, com correlação de 0,70 (p < 0,001), e artefato de imagem na fases em contraste,com correlação de 0,73 (p < 0,001). Ao avaliar a habilidade de predizer artefato de imagem baixo, as áreas sob a curva ROC para o artefato de imagem na fases em contraste e para a espessura pele-esterno foram 0,837e 0,864, respectivamente. Conclusão: Tanto espessura pele-esterno quanto artefato de escore de cálcio são preditores simples e precisos de artefato de imagem em ATCC. Tais parâmetros podem ser incorporados aos protocolos de TC padrão para ajustar adequadamente a exposição à radiação.

Microhabitats de mosquitos (Diptera, Culicidae) em internódios de taquara na Mata Atlântica, Paraná, Brasil

During two consecutive years, from January 1985 to December 1986, a comparative study of mosquitoes preferences for breeding habitat was carried out in the Atlantic Forest of the Serra do Mar, Paraná State, Brazil. To achieve it, 1875 bamboo internodes aligned vertically in live green, bamboo plants Merostachys speciosa Munro and Merostachys sp. were used, in which metabolic water was exuded from the plant itself, and presenting different size/pattern holes at their lateral walls, bored by the local sylvan fauna. Another group of 1200 individual internode traps was used as comparative element, carved out with a transversal cut by a saw, filled with local stream water and held in branches at different heights in the vegetal strata nearby. At both microhabitat types, a total of 17 culicid species was registered. Culex (Microculex) neglectus Lutz, 1904, Cx. (Carrollia) soperi Antunes & Lane, 1937, Sabethes (Sabethes) batesi Lane & Cerqueira, 1942 and Sa. (Sabethinus) melanonymphe (Dyar, 1924)colonized exclusively live plant internodes, while Culex (Microculex) elongatus Rozeboom & Lane, 1950, Cx. (Carrollia) iridescens (Lutz, 1905), Cx. (Carrollia) kompi Valencia,1973and Trichoprosopon (Trichoprosopon) soaresi Dyar & Knab, 1907 bred only in internode traps. The remaining nine species colonized both habitats indistinctly. Quantitatively, was detected the abundance of 60.1% at live green internodes, against 39.9% for internode traps. Concerning the different patterns of bored live internode holes, 40.3% of the total computed specimens were collected in square or rectangular holes, 31.9% in two hole internodes, one minute circular, the other wider, and the remaining 28.8% of specimens distributed in other pattern type internodes. The mosquitoes breeding at these microhabitats fall in the culicid entomofauna specialized at locating and detecting peculiar and propitious mesogen conditions for breeding purposes.

Sinopse dos gêneros Scopadus e Omosarotes (Coleoptera, Cerambycidae, Lamiinae)

Descriptions, synonym, new combinations and key to the species of Omosarotes Pascoe, 1860 are given. The male of Scopadus ciliatus Pascoe, 1857 is described. New species described: Omosarotes ater (type locality: Santo Domingo de los Colorados, Ecuador). New synonym proposed: Acanthomerosternoplon Tippmann, 1955 with Omosarotes Pascoe, 1860. New combinations: Omosarotes nigripennis (Zajciw, 1970) (from Scopadus Pascoe, 1857), O. paradoxum (Tippmann, 1955) and O. foxi (Lane, 1973), both from Acanthomerosternoplon Tippmann, 1955.

Novo gênero de Anacolini e descrição dos machos de Myzomorphus Flavipes e Poekilosoma Carinatipenne (Coleoptera, Cerambycidae, Prioninae)

The new genus Hovorelus and its type-species, H. splendidus sp. nov., are described from Peru. The males of Myzomorphus flavipes Galileo, 1987 and Poekilosoma carinatipenne Lane, 1941, both with sexual dimorphism, are described for the first time.

Revalidação de Mauesini (Coleoptera, Cerambycidae, Lamiinae), transferência de gêneros, sinonímias e novos táxons

The tribe Mauesini Lane, 1956 is revalidated (type genus, Mauesia Lane, 1956). The following genera are transferred from Anisocerini to Mauesini: Taurolema Thomson, 1860 and Coroicoia Lane, 1966. New synonyms proposed: Taurolema nasicornis Schwarzer, 1930 with T. albopunctata Gounelle, 1906 and T. lineata Fuchs, 1966 with T. cicatricosa Lane, 1966. New species described from Brazil: Taurolema nigropilosa (Espírito Santo); Mauesia bicornis and M. acorniculata (both from Amazonas). A key to the genera of Mauesini is added.

Revisão do gênero Natagaima (Coleoptera, Cerambycidae, Lamiinae)

Natagaima Lane, 1972 is revised and provisionally transferred from Anisocerini to Acanthoderini. The genus and the type species, Natagaima balteata Lane, 1972, are redescribed and two new species added: N. moacyri, from Colombia (Tumaco) and N. heloisae, from Ecuador (Napo). All the species are illustrated and keyed.

Revisão do gênero Satipoella (Coleoptera, Cerambycidae, Lamiinae)

The genus Satipoella Lane, 1964 is revised and a new synonym is proposed, Icarai Galileo & Martins, 1998, with Satipoella. A new species, S. ochroma, is described from Amazonas, Brazil. New combination: Satipoella bufo (Thomson, 1864) from Icarai. The three species of Satipoella are illustrated and keyed.

Contribuição aos Hemilophini (Cerambycidae, Lamiinae) da Colômbia e do Equador

New taxa described: from Ecuador, Quirimbaua gen. nov., type species Q. castroi (Napo); from Colombia: Icupima taua (Cauca), Adesmus murutinga and Tyrinthia dioneae (Valle del Cauca), Essosthrutella acatinga and Hemilomecopterus gen. nov., type species, H. alienus (Amazonas). New records for Colombia are presented for Olivensa mimula Lane, 1965, Tyrinthia paraba Martins & Galileo, 1991, Amapanesia exotica (Martins & Galileo, 1991), Sibapipunga beckeri (Martins & Galileo, 1992), Juninia annulifera (Kirsch, 1889), Isomerida albicollis (Laporte, 1840), Adesmus diana (Thomson, 1860), A. pirauna Galileo & Martins, 1999, Phoebe concinna White, 1856 and Leucophoebe albaria (Bates, 1872). A key to the species of Essosthrutella is added.

Novos Hemilophini (Coleoptera, Cerambycidae, Lamiinae) da Região Neotropical

A key to the species of Murupeaca Martins & Galileo, 1992 is presented and M. tavakiliani, from French Guyana, is described. Hemiloapis gen. nov. and its type-species, H. yandaira sp. nov. are described from Bolivia.Two new species are described in the genus Mariliana Lane, 1970, M. amazonica sp. nov. from French Guiana and M. cicadellida sp. nov. from Bolivia. A key to the species of Mariliana is added. Two other new species of the genus Erana Bates, 1866 are described: E. septuosa sp. nov. and E. rosea sp. nov., both from Panama.

Sinopse do gênero Xylergates (Cerambycidae, Lamiinae, Acanthocinini)

Uma sinopse do gênero Xylergates Bates, 1864 é apresentada. O seguinte sinônimo é estabelecido: Xylergatina Gilmour, 1962 = Xylergates Bates, 1864 e o novo restabelecimento de Xylergates pulcher Lane, 1957. Uma nova espécie do Espírito Santo (Brazil) é descrita, Xylergates capixaba. Uma chave para espécies é adicionada.