Determination of pesticide residues in coconut water by liquid-liquid extraction and gas chromatography with electron-capture plus thermionic specific detection and solid-phase extraction and high-performance liquid chromatography with ultraviolet detection

Two simple methods were developed to determine, 11 pesticides in coconut water, a natural isotonic drink rich in salts, sugars and vitamins consumed by the people and athletes. The first procedure involves solid-phase extraction using Sep-Pak Vac C-18 disposable cartridges with methanol for elution. Isocratic analysis was carried out by means of high-performance liquid chromatography with ultraviolet detection at 254 nm to analyse captan, chlorothalonil, carbendazim, lufenuron and diafenthiuron. The other procedure is based on liquid-liquid extraction with hexane-dichloromethane (1:1, v/v), followed by gas chromatographic analysis with effluent splitting to electron-capture detection for determination of endosulfan, captan, tetradifon and trichlorfon and thermionic specific detection for determination of malathion, parathion-methyl and monocrotophos. The methods were validated with fortified samples at different concentration levels (0.01-12.0 mg/kg). Average recoveries ranged from 75 to 104% with relative standard deviations between 1.4 and 11.5%. Each recovery analysis was repeated at least five times. Limits of detection ranged from 0.002 to 2.0 mg/kg. The analytical procedures were applied to 15 samples and no detectable amounts of the pesticides were found in any samples under the conditions described. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Determinantes de la inversión en el sector petróleo y gas en la Argentina

Incluye Bibliografía

Desarrollo del gas lutita (shale gas) y su impacto en el mercado energético: reflexiones para Centroamérica

La producción de shale gas o gas natural de lutita en los Estados Unidos ha sorprendido al mundo por su rápido desarrollo y repercusión en la disminución del precio del combustible y el aumento de reservas de hidrocarburos. Este desarrollo ha crecido junto con la oferta de petróleo y de condensados de gas natural. Se estima que los Estados Unidos serían autosuficientes en petróleo y superavitarios en gas natural en menos de 30 años. El renovado impulso de los hidrocarburos no-convencionales empieza a ser visto como una "revolución energética" que dará nuevo dinamismo a la economía de ese país. Por su novedad, la evaluación completa de estos desarrollos confronta dificultades metodológicas, estadísticas y de conocimiento científico, tecnológico, social y económico. Las regiones de los Estados Unidos y Canadá con yacimientos de shale gas comprobados son muchas. Sin embargo, dado lo novedoso de su explotación, no existe historial suficientemente largo para sacar conclusiones sobre procesos de exploración, picos y declives de producción y técnicas de recuperación de los recursos. Las analogías y extrapolaciones de las experiencias varían entre plays o conglomerados de yacimientos. Las dudas crecen ante la discordancia entre la creciente producción de gas y precios de mercado inferiores a los costos. También se escuchan advertencias sobre los potenciales efectos nocivos de su explotación en el medio ambiente y comunidades aledañas. Hay dudas sobre los posibles efectos de la técnica de "fracturamiento hidráulico" (fracking) y los disolventes químicos empleados en mantos freáticos y agua potable. Este documento se compone de cinco capítulos. En el primero se aborda el tema de la explotación de shale gas, desde el origen, la producción, la economía y los impactos de la exploración y producción de shale gas, hasta algunas peculiaridades del entorno de negocios y de los sistemas legal, financiero e impositivo. Dada su vasta experiencia en producción de hidrocarburos, los Estados Unidos cuentan con numerosas empresas proveedoras de bienes y servicios para la exploración y explotación de shale gas. Legisladores y autoridades de todos los niveles aplican instrumentos legales y procesan debates y opiniones para ir encontrando soluciones a los retos y cuestionamientos relacionados. En el capítulo II se presenta un análisis de escenarios y proyecciones al año 2035. Se discuten las dinámicas que pueden convertir a los Estados Unidos en exportador neto de gas natural. Se asume que el energético menos costoso termina dominado el mercado. Sin embargo, el shale gas tiene un largo proceso por recorrer antes de desbancar a las grandes industrias de energía con muchas décadas en el mercado. Se revisa el crecimiento de reservas y producción en abasto a una demanda creciente, que a su vez requerirá que los sistemas de transporte, almacenamiento y distribución de combustible se sigan expandiendo y que los precios de mercado continúen bajos o aumenten lentamente, mientras los del crudo serían sustancialmente mayores. Esta diferencia de precios está motivando la sustitución de combustibles. Las tecnologías de "gas a líquidos", "gas comprimido", "celdas de gas metano" y otras seguirán abriendo espacio, hasta sustituir las tecnologías basadas en hidrocarburos líquidos que han dominado el desarrollo energético por más de un siglo. La etapa de transición hacia lo que los teóricos consideran que será la era de los energéticos renovables se está volviendo realidad. Pero no hay indicios de que los combustibles tradicionales simplemente desaparecerán para dar paso a los energéticos renovables. Más bien, el shale gas se desarrolla como una nueva capa tendiente a envolver todo el mercado, sobre la cual se irá acomodando gradualmente el resto de los energéticos renovables. Así está sucediendo ya en la industria eléctrica debido a la flexibilidad de los ciclos combinados basados en gas natural, en especial su capacidad de reducir e incrementar su carga, conservando altos rendimientos térmicos. Esta flexibilidad permitirá que el resto de las fuentes alternativas (eólica, solar, mareomotriz y las que se vayan incorporando), cuya capacidad de generación es variable, se acomoden en forma combinada. En el III capítulo se describe la situación del gas natural en México, donde los bajos precios del combustible, el avance tecnológico, el manejo político del marco legal ambiental y social, además de la expansión de las redes de transporte, almacenamiento y distribución, también están cambiando. Se espera que el shale gas sea una nueva fuente de riqueza y de energía a bajo costo, pero, el proceso tomará varios años o décadas antes de que las expectativas se hagan realidad. Existen dudas sobre la forma de materializar este potencial en el país. Un primer problema para México es su propia definición constitucional de la propiedad y explotación de los hidrocarburos por un monopolio de Estado, Pemex. Este modelo resulta inadecuado para explotar shale gas a gran escala. Otro problema está representado por los altos costos de logística presionados por la rapidez del ciclo de producción, cuyos picos y declives se alcanzan a pocas semanas de iniciada la perforación. El declive puede ser tan rápido hasta volver incosteable mantener los equipos en un solo lugar por demasiado tiempo. Pemex no parece adaptada para trabajar en una dinámica logística de gran velocidad, en la que los equipos de perforación y de trabajadores deben desplazarse entre numerosas operaciones. Por estas razones, México parece destinado a experimentar una primera etapa consumiendo shale gas barato importado de los Estados Unidos. Para ello se construyen redes de gasoductos a lo largo de la frontera, por donde se irá recibiendo el gas y acostumbrándose a él. Después vendrán los grandes debates nacionales para decidir quiénes serán los protagonistas de este nuevo desarrollo, si Pemex o empresas privadas. Las reformas resultantes deberán plasmarse en la Constitución y reglamentarse en leyes secundarias; se diseñarán nuevos modelos impositivos y regulatorios. A esto se agregará la preocupación por los impactos sociales y ambientales de esta industria, la escasez de proveedores especializados y la necesidad de capacitar gran número de trabajadores, los cuales podrían ser contratados por Pemex o por el sector privado, dependiendo del modelo que se adopte en las reformas. El ritmo de aprovechamiento del shale gas mexicano será lento. Este reto no ha sido discutido en México. Se habla de los reacomodos del mercado de gas natural como fenómeno de corto plazo, referido a los precios presentes. Mientras tanto, el desabasto de gas natural se convierte en tema central de la política industrial. ¿Quién pagará el sobreprecio del gas natural licuado (LNG) en las escasas terminales de regasificación del país? En el capítulo IV se presenta el balance de exportaciones e importaciones de gas natural de América del norte. El reto de México a mediano plazo se perfila como la necesidad de desarrollar su propia industria gasera y extender las redes de gasoductos y de electricidad, hasta unir el sur y el norte del país, desarrollando simultáneamente la región oeste en la costa del Pacífico. Con el gas natural como punta de lanza, la industria energética irá configurando una nueva geografía industrial. Ahora corresponde al sistema político crear las condiciones institucionales para que esa dinámica se extienda por todo el territorio nacional. En el capítulo V se abordan algunas implicaciones y retos para los países de Centroamérica. Se discute la posibilidad de consolidar consorcios regionales sólidos, capaces de negociar contratos con México para abastecer gas natural a largo plazo, además de financiar los gasoductos necesarios. También se analizan algunos escenarios favorables en el caso de la negociación de suministros de gas natural en el marco de los tratados de libre comercio que los países de dicha subregión tienen con los Estados Unidos.

Impactos ambientais decorrentes de vazamento de gás natural de baixa e média pressões, na área urbana central do município de São Paulo

Pós-graduação em Geociências e Meio Ambiente - IGCE

Sistema de controle de escoamento de gás natural em dutos de distribuição com detecção de vazamentos utilizando redes neurais

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Chemical Characterization and Antimicrobial Activity Evaluation of Natural Oil Nanostructured Emulsions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise comparativa entre a produção de biogás em aterro controlado e variações no potencial elétrico natural por meio de perfilagem geofísica

This work aims to analyze data from a Natural Electric Potential landfill type ditch located in Cordeirópolis (SP). The procedure measures initially involved the assembly and installation of an apparatus cables, sensors and drain geophysical measurements and flow rate of biogas in a ditch later filled by solid waste. Biogas is a product of degradation of organic matter in waste by the action of microorganisms in an anaerobic environment. Its features high methane content in the gas potentially usable as fuel in energy generation systems or steam. The study area is characterized by clayey soil composition change from the diabase sill correlated to the event Serra Geral Formation siltstones overlapping Tatuí with groundwater level site around 50m. The cables were installed vertically in parallel with drain gas manifold, which allowed the collection of data by the technique geophysical logging every 15 days over a period of eight months. For data analysis we used four parameters in the study, the closing time of the ditch, natural electric potential, the flow velocity of biogas and rain. With the tabulated data plots were constructed for each collection day showing values in the range of the cable is in contact with waste (200 cm - 400 cm) and range of the cable in contact with the soil (600 cm - 800 cm). Subsequently graphs were generated with the period of eight months to analyze the data tabulated. A statistical correlation data, which show the influence of rainfall on the production of biogas. The results were satisfactory and demonstrated the feasibility of the research method in studies for the feasibility analysis for the capture of biogas energy

Gasolina, gás natural e etanol: comparação dos principais impactos ambientais da produção ao consumo final

Não disponível.

Leaf gas exchange and yield of three upland rice cultivars

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Online analysis of H2S and SO2 via advanced mid-Infrared gas sensors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Vulnerabilidade natural e risco à contaminação do aquífero livre da área urbana de Rio Claro - SP

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Morphology of the gas bladder in thorny catfishes (Siluriformes: Doradidae)

The gross morphology of the gas bladder is described, illustrated, compared and categorized among 86 of 88 nominal valid and six undescribed species representing all 31 genera of Doradidae with comments on ontogenetic and taxonomic variation when observed. The putatively basal-most doradids exhibit an unmodified cordiform gas bladder. Derived taxa exhibit an impressive suite of modifications including the addition of a secondary bladder, pronounced reduction of the posterolateral chambers, internal trabeculae, associations with bony capsule-like expansions of the anterior (Weberian) vertebrae, and accessory diverticula varying widely in size, shape, abundance, and distribution. Intra-specific differences are minor, most often reflective of ontogenetic changes especially in large-size species, whereas inter-specific and inter-generic differences are significant, in many cases diagnostic, and suggestive of phylogenetic signal excepting instances of evident convergence such as gas bladder reduction in Rhynchodoras and all but one species of Leptodoras.

Gas-phase reactivity of 2-hydroxy-1,4-naphthoquinones: a computational and mass spectrometry study of lapachol congeners

In order to understand the influence of alkyl side chains on the gas-phase reactivity of 1,4-naphthoquinone derivatives, some 2-hydroxy-1,4-naphthoquinone derivatives have been prepared and studied by electrospray ionization tandem mass spectrometry in combination with computational quantum chemistry calculations. Protonation and deprotonation sites were suggested on the basis of gas-phase basicity, proton affinity, gas-phase acidity (?Gacid), atomic charges and frontier orbital analyses. The nature of the intramolecular interaction as well as of the hydrogen bond in the systems was investigated by the atoms-in-molecules theory and the natural bond orbital analysis. The results were compared with data published for lapachol (2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone). For the protonated molecules, water elimination was verified to occur at lower proportion when compared with side chain elimination, as evidenced in earlier studies on lapachol. The side chain at position C(3) was found to play important roles in the fragmentation mechanisms of these compounds. Copyright (c) 2012 John Wiley & Sons, Ltd.

Natural patterns and anthropogenic disturbance in north Adriatic marine benthic assemblages: descriptive and methodological studies

Marine soft bottom systems show a high variability across multiple spatial and temporal scales. Both natural and anthropogenic sources of disturbance act together in affecting benthic sedimentary characteristics and species distribution. The description of such spatial variability is required to understand the ecological processes behind them. However, in order to have a better estimate of spatial patterns, methods that take into account the complexity of the sedimentary system are required. This PhD thesis aims to give a significant contribution both in improving the methodological approaches to the study of biological variability in soft bottom habitats and in increasing the knowledge of the effect that different process (both natural and anthropogenic) could have on the benthic communities of a large area in the North Adriatic Sea. Beta diversity is a measure of the variability in species composition, and Whittaker’s index has become the most widely used measure of beta-diversity. However, application of the Whittaker index to soft bottom assemblages of the Adriatic Sea highlighted its sensitivity to rare species (species recorded in a single sample). This over-weighting of rare species induces biased estimates of the heterogeneity, thus it becomes difficult to compare assemblages containing a high proportion of rare species. In benthic communities, the unusual large number of rare species is frequently attributed to a combination of sampling errors and insufficient sampling effort. In order to reduce the influence of rare species on the measure of beta diversity, I have developed an alternative index based on simple probabilistic considerations. It turns out that this probability index is an ordinary Michaelis-Menten transformation of Whittaker's index but behaves more favourably when species heterogeneity increases. The suggested index therefore seems appropriate when comparing patterns of complexity in marine benthic assemblages. Although the new index makes an important contribution to the study of biodiversity in sedimentary environment, it remains to be seen which processes, and at what scales, influence benthic patterns. The ability to predict the effects of ecological phenomena on benthic fauna highly depends on both spatial and temporal scales of variation. Once defined, implicitly or explicitly, these scales influence the questions asked, the methodological approaches and the interpretation of results. Problem often arise when representative samples are not taken and results are over-generalized, as can happen when results from small-scale experiments are used for resource planning and management. Such issues, although globally recognized, are far from been resolved in the North Adriatic Sea. This area is potentially affected by both natural (e.g. river inflow, eutrophication) and anthropogenic (e.g. gas extraction, fish-trawling) sources of disturbance. Although few studies in this area aimed at understanding which of these processes mainly affect macrobenthos, these have been conducted at a small spatial scale, as they were designated to examine local changes in benthic communities or particular species. However, in order to better describe all the putative processes occurring in the entire area, a high sampling effort performed at a large spatial scale is required. The sedimentary environment of the western part of the Adriatic Sea was extensively studied in this thesis. I have described, in detail, spatial patterns both in terms of sedimentary characteristics and macrobenthic organisms and have suggested putative processes (natural or of human origin) that might affect the benthic environment of the entire area. In particular I have examined the effect of off shore gas platforms on benthic diversity and tested their effect over a background of natural spatial variability. The results obtained suggest that natural processes in the North Adriatic such as river outflow and euthrophication show an inter-annual variability that might have important consequences on benthic assemblages, affecting for example their spatial pattern moving away from the coast and along a North to South gradient. Depth-related factors, such as food supply, light, temperature and salinity play an important role in explaining large scale benthic spatial variability (i.e., affecting both the abundance patterns and beta diversity). Nonetheless, more locally, effects probably related to an organic enrichment or pollution from Po river input has been observed. All these processes, together with few human-induced sources of variability (e.g. fishing disturbance), have a higher effect on macrofauna distribution than any effect related to the presence of gas platforms. The main effect of gas platforms is restricted mainly to small spatial scales and related to a change in habitat complexity due to a natural dislodgement or structure cleaning of mussels that colonize their legs. The accumulation of mussels on the sediment reasonably affects benthic infauna composition. All the components of the study presented in this thesis highlight the need to carefully consider methodological aspects related to the study of sedimentary habitats. With particular regards to the North Adriatic Sea, a multi-scale analysis along natural and anthopogenic gradients was useful for detecting the influence of all the processes affecting the sedimentary environment. In the future, applying a similar approach may lead to an unambiguous assessment of the state of the benthic community in the North Adriatic Sea. Such assessment may be useful in understanding if any anthropogenic source of disturbance has a negative effect on the marine environment, and if so, planning sustainable strategies for a proper management of the affected area.

Application of comprehensive gas chromatography (GCxGC) to measurements of volatile organic species in ambient air

The focus of this thesis was the in-situ application of the new analytical technique "GCxGC" in both the marine and continental boundary layer, as well as in the free troposphere. Biogenic and anthropogenic VOCs were analysed and used to characterise local chemistry at the individual measurement sites. The first part of the thesis work was the characterisation of a new set of columns that was to be used later in the field. To simplify the identification, a time-of-flight mass spectrometer (TOF-MS) detector was coupled to the GCxGC. In the field the TOF-MS was substituted by a more robust and tractable flame ionisation detector (FID), which is more suitable for quantitative measurements. During the process, a variety of volatile organic compounds could be assigned to different environmental sources, e.g. plankton sources, eucalyptus forest or urban centers. In-situ measurements of biogenic and anthropogenic VOCs were conducted at the Meteorological Observatory Hohenpeissenberg (MOHP), Germany, applying a thermodesorption-GCxGC-FID system. The measured VOCs were compared to GC-MS measurements routinely conducted at the MOHP as well as to PTR-MS measurements. Furthermore, a compressed ambient air standard was measured from three different gas chromatographic instruments and the results were compared. With few exceptions, the in-situ, as well as the standard measurements, revealed good agreement between the individual instruments. Diurnal cycles were observed, with differing patterns for the biogenic and the anthropogenic compounds. The variability-lifetime relationship of compounds with atmospheric lifetimes from a few hours to a few days in presence of O3 and OH was examined. It revealed a weak but significant influence of chemistry on these short-lived VOCs at the site. The relationship was also used to estimate the average OH radical concentration during the campaign, which was compared to in-situ OH measurements (1.7 x 10^6 molecules/cm^3, 0.071 ppt) for the first time. The OH concentration ranging from 3.5 to 6.5 x 10^5 molecules/cm^3 (0.015 to 0.027 ppt) obtained with this method represents an approximation of the average OH concentration influencing the discussed VOCs from emission to measurement. Based on these findings, the average concentration of the nighttime NO3 radicals was estimated using the same approach and found to range from 2.2 to 5.0 x 10^8 molecules/cm^3 (9.2 to 21.0 ppt). During the MINATROC field campaign, in-situ ambient air measurements with the GCxGC-FID were conducted at Tenerife, Spain. Although the station is mainly situated in the free troposphere, local influences of anthropogenic and biogenic VOCs were observed. Due to a strong dust event originating from Western Africa it was possible to compare the mixing ratios during normal and elevated dust loading in the atmosphere. The mixing ratios during the dust event were found to be lower. However, this could not be attributed to heterogeneous reactions as there was a change in the wind direction from northwesterly to southeasterly during the dust event.