Analysis of 'APN' naphthenic acids by high temperature gas chromatoagraphy and high performance liquid chromatography

Examination by high temperature GC (HTGC) of the methyl esters of the so-called 'ARN' naphthenic acids from crude oils of North Sea UK, Norwegian Sea and West African oilfields revealed the distributions of resolved 4-8 ring C-80 tetra acids and trace amounts of other acids. Whilst all three oils contained apparently the same the proportions of each differed, possibly reflecting the growth tempe acids, ratures of the archaebacteria from which the acids are assumed to have originated. The structures of the 4, 5, 7 and 8 ring acids are tentatively assigned by comparison with the known 6 ring acid and related natural products and an HPLC method for the isolation of the individual acids is described. ESI-MS of individual acids isolated by preparative HPLC established the elution order of the 4-8 ring acids on the HPLC and HTGC systems and revealed the presence of previously unreported acids tentatively identified as C-81 and C-82 7 and 8 ring analogues.

The use of colloidal gas aphrons as novel downstream processing for the recovery of astaxanthin from cells of Phaffia rhodozyma

BACKGROUND: There is an increasing interest in obtaining natural products with bioactive properties, using fermentation technology. However, the downstream processing consisting of multiple steps can be complicated, leading to increase in the final cost of the product. Therefore there is a need for integrated, cost-effective and scalable separation processes. RESULTS: The present study investigates the use of colloidal gas aphrons (CGA), which are surfactant-stabilized microbubbles, as a novel method for downstream processing. More particularly, their application for the recovery of astaxanthin from the cells of Phaffia rhodozyma is explored. Research carried out with standard solutions of astaxanthin and CGA generated from the cationic surfactant hexadecyl. trimethyl ammonium bromide (CTAB) showed that up to 90% recovery can be achieved under optimum conditions, i.e., pH 11 with NaOH 0.2 mol L-1. In the case of the cells' suspension from the fermentation broth, three different approaches were investigated: (a) the conventional integrated approach where CGA were applied directly; (b) CGA were applied to the clarified suspension of cells; and finally (c) the in situ approach, where CGA are generated within the clarified suspension of cells. Interestingly, in the case of the whole suspension (approach a) highest recoveries (78%) were achieved under the same conditions found to be optimal for the standard solutions. In addition, up to 97% recovery of total carotenoids could be achieved from the clarified suspension after pretreatment with NaOH. This pretreatment led to maximum cell disruption as well as optimum conditioning for subsequent CGA separation. CONCLUSIONS: These results demonstrate the potential of CGA for the recovery of bioactive components from complex feedstock. (c) 2008 Society of Chemical Industry.

Foraging strategies of natural enemies of the peach-potato aphid Myzus persicae

The foraging strategies of two natural enemies of the peach-potato aphid Myzus persicae: the seven-spot ladybird Coccinella septempunctata and the parasitoid wasp Diaeretiella rapae, were investigated. Specifically the roles of plant semiochemicals in the location of plants infested with M. persicae by these natural enemies were examined. I investigated the olfactory responses of female C. septempunctata to volatiles collected from M. persicae and four Brassica cultivars; Brassica rapa, B. juncea, B. napus cultivar ‘Apex’ and B. napus cultivar ‘Courage’ and wild-type Arabidopsis thaliana that were: undamaged, previously infested by M. persicae and infested with M. persicae. C. septempunctata showed no attraction to volatiles from M. persicae alone. C. septempunctata significantly changed its searching behaviour in response to plant volatiles from B. rapa, B. napus cv. ‘Apex’ and Arabidopsis infested with M. persicae. C. septempunctata was also found to display a significant turning bias when foraging on a branching horizontal wire stem. A model was developed to investigate how turning biases affect the foraging efficiency of C. septempunctata in dichotomous branched environments. Simulations using this model indicated that turning biases could potentially increase searching efficiency. D. rapae showed a significant preference for volatiles from M. persicae infested wild-type Arabidopsis but no preference to volatiles from M. persicae alone or M. persicae honeydew. Volatile emissions by Arabidopsis were shown to be localised to the area of aphid-infestation rather than systemic. Using gas chromatography plants infested with M. persicae were shown to emit a quantitatively different volatile blend than undamaged plants. In experiments with jasmonate mutants of Arabidopsis the jasmonate (octadecanoid) wound response pathway was implicated as being important for the production of M. persicae induced volatiles, attractive to D. rapae. Other wound response pathways were also found to be involved in the production of the full blend of M. persicae induced volatiles.

A green flow-based procedure for fluorimetric determination of acid-dissociable cyanide in natural waters exploiting multicommutation

A flow system designed with solenoid valves is proposed for determination of weak acid dissociable cyanide, based on the reaction with o-phthalaldehyde (OPA) and glycine yielding a highly fluorescent isoindole derivative. The proposed procedure minimizes the main drawbacks related to the reference batch procedure, based on reaction with barbituric acid and pyridine followed by spectrophotometric detection, i.e., use of toxic reagents, high reagent consumption and waste generation, low sampling rate, and poor sensitivity. Retention of the sample zone was exploited to increase the conversion rate of the analyte with minimized sample dispersion. Linear response (r=0.999) was observed for cyanide concentrations in the range 1-200 mu g L(-1), with a detection limit (99.7% confidence level) of 0.5 mu g L(-1)(19 nmol L(-1)). The sampling rate and coefficient of variation (n=10) were estimated as 22 measurements per hour and 1.4%, respectively. The results of determination of weak acid dissociable cyanide in natural water samples were in agreement with those achieved by the batch reference procedure at the 95% confidence level. Additionally to the improvement in the analytical features in comparison with those of the flow system with continuous reagent addition (sensitivity and sampling rate 90 and 83% higher, respectively), the consumption of OPA was 230-fold lower.

Pendimethalin determination in natural water, baby food and river sediment samples using electroanalytical methods

This work describes the electroanalytical determination of pendimethalin herbicide levels in natural waters, river sediment and baby food samples, based on the electro-reduction of herbicide on the hanging mercury drop electrode using square wave voltammetry (SWV). A number of experimental and voltammetric conditions were evaluated and the best responses were achieved in Britton-Robinson buffer solutions at pH 8.0, using a frequency of 500 s(-1). a scan increment of 10 mV and a square wave amplitude of 50 mV. Under these conditions, the pendimethalin is reduced in an irreversible process, with two reduction peaks at -0.60 V and -0.71 V. using a Ag/AgCl reference system. Analytical curves were constructed and the detection limit values were calculated to be 7.79 mu g L(-1) and 4.88 mu g L(-1), for peak 1 and peak 2, respectively. The precision and accuracy were determinate as a function of experimental repeatability and reproducibility, which showed standard relative deviation values that were lower than 2% for both voltammetric peaks. The applicability of the proposed methodology was evaluated in natural water, river sediments and baby food samples. The calculated recovery efficiencies demonstrate that the proposed methodology is suitable for determining any contamination by pendimethalin in these samples. Additionally, adsorption isotherms were used to evaluate information about the behavior of pendimethalin in river sediment samples. (C) 2010 Elsevier B.V. All rights reserved.

Desenhos de mercado de gás natural e o caso brasileiro

Este trabalho tem como objetivo analisar os principais fatores envolvidos no desenvolvi- mento e funcionamento da indústria de gás natural, para então detectar e diagnosticar as principais falhas existentes no mercado brasileiro de gás. A análise é realizada a partir da caracterização dos diversos desenhos de mercado da indústria de gás natural presentes no mundo (desde a estrutura totalmente verticalizada até a mais competitiva, com a presença de mercados de atacado e varejo). Pontos importantes são ressaltados tais como os princípios de precificação do gás em cada modelo, as práticas regulatórias empregadas e as principais estruturas surgidas. Destas, destacam-se as relações entre os agentes nos mercados de varejo competitivos, o livre acesso, o bypass físico e comercial e o surgimento do mercado spot. Essa linha de trabalho culmina com a análise da atual estrutura do mercado de gás natural no Brasil, assim como possíveis desenhos que essa indústria poderá atingir a médio e longo prazos dependendo dos mecanismos regulatórios utilizados. Para isso, são apresentados os modelos de gás existentes e a interação entre eles. Ressalta-se, também, a importância do livre acesso para o desenvolvimento do setor no Brasil.

Estudo da molhabilidade de tecidos 100% poliéster tratados em plasma N2/O2 em função do seu envelhecimento natural

This work reports the influence of the poly (ethylene terephthalate) textile surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min. Other parameters, such as working gas composition and treatment time, were modified as the following: to the O2 plasma modified samples only the treatment time was changed (10, 20, 30, 40, 50 and 60 minutes). To the plasma with O2 and N2 only the chemical concentrations were changed. Through Capillary tests (vertical) an increase in textile wettability was observed as well as its influence on aging time and its consequence on wettability. The surface functional groups created after plasma treatments were investigated using X-ray Photoelectron Spectroscopy (XPS). The surface topography was examined by scanning electron microscope (SEM)

Sistemas de medição de desempenho para projetos de PD&I no Setor de Petróleo e Gás Natural

Organizations are seeking new ideas, tools and methods aiming to improve management process and performance. On the other hand, system performance measurement needs to portray organizational changes and provide managers with a set of true and more appropriate information for the decision-making process. This work aims to propose a performance measurement system in the academic field regarding Research, Development and Innovation (RDI) in the oil and gas industry. The research performed a bibliographic review in a descriptive exploratory manner. A field research was conducted with an expert focus group in order to gather new indicators. As for the validation of these indicators, a survey with experienced professional was also realized. The research surveyed four segments in and outside of the Federal University of Rio Grande do Norte-Brazil such as oil and gas project coordinators, staff at Academic Planning Offices, FUNPEC employees as well as coordinators from Petrobrás. The performance measuring system created from this study features three interrelated performance indicators pointed out as: process indicators, outcome indicators and global indicators. The proposal includes performance indicators that seek to establish more appropriate strategies for effective institution management. It might help policy making of university-industry interaction policies

Ultraviolet-B and water stress effects on growth, gas exchange and oxidative stress in sunflower plants

The effects and interaction of drought and UV-B radiation were studied in sunflower plants (Helianthus annuus L. var. Catissol-01), growing in a greenhouse under natural photoperiod conditions. The plants received approximately 1.7 W m(-2) (controls) or 8.6 W m(-2) (+UV-B) of UV-B radiation for 7 h per day. The UV-B and water stress treatments started 18 days after sowing. After a period of 12 days of stress, half of the water-stressed plants (including both UV-B irradiated or non-irradiated) were rehydrated. Both drought and UV-B radiation treatments resulted in lower shoot dry matter per plant, but there was no significant interaction between the two treatments. Water stress and UV-B radiation reduced photosynthesis, stomatal conductance and transpiration. However, the amplitude of the effects of both stressors was dependent on the interactions. This resulted in alleviation of the negative effect of drought on photosynthesis and transpiration by UV-B radiation as the water stress intensified. Intercelluar CO(2) concentration was initially reduced in all treatments compared to control plants but it increased with time. Photosynthetic pigments were not affected by UV-B radiation. Water stress reduced photosynthetic pigments only under high UV-B radiation. The decrease was more accentuated for chlorophyll a than for chlorophyll b. As a measure for the maximum efficiency of photosystem II in darkness F (v)/F (m) was used, which was not affected by drought stress but initially reduced by UV-B radiation. Independent of water supply, UV-B radiation increased the activity of pirogalol peroxidase and did not increase the level of malondialdehyde. on the other hand, water stress did not alter the activity of pirogalol peroxidase and caused membrane damage as assessed by lipid peroxidation. The application of UV-B radiation together with drought seemed to have a protective effect by lowering the intensity of lipid peroxidation caused by water stress. The content of proline was not affected by UV-B radiation but was increased by water stress under both low and high UV-B radiation. After 24 h of rehydration, most of the parameters analyzed recovered to the same level as the unstressed plants.

Development of environmental and natural vulnerability maps for Brazilian coastal at Sao Sebastiao in São Paulo State

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Quality of the forage apparently consumed by beef calves in natural grassland under fertilization and oversown with cool season forage species

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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