Design, construction and evaluation of a simple pressurized solvent extraction system

This work describes the construction and testing of a simple pressurized solvent extraction (PSE) system. A mixture of acetone:water (80:20), 80 ºC and 103.5 bar, was used to extract two herbicides (Diuron and Bromacil) from a sample of polluted soil, followed by identification and quantification by high-performance liquid chromatography coupled with diode array detector (HPLC-DAD). The system was also used to extract soybean oil (70 ºC and 69 bar) using pentane. The extracted oil was weighed and characterized through the fatty acid methyl ester analysis (myristic (< 0.3%), palmitic (16.3%), stearic (2.8%), oleic (24.5%), linoleic (46.3%), linolenic (9.6%), araquidic (0.3%), gadoleic (< 0.3%), and behenic (0.3%) acids) using high-resolution gas chromatography with flame ionization detection (HRGC-FID). PSE results were compared with those obtained using classical procedures: Soxhlet extraction for the soybean oil and solid-liquid extraction followed by solid-phase extraction (SLE-SPE) for the herbicides. The results showed: 21.25 ± 0.36% (m/m) of oil in the soybeans using the PSE system and 21.55 ± 0.65% (m/m) using the soxhlet extraction system; extraction efficiency (recovery) of herbicides Diuron and Bromacil of 88.7 ± 4.5% and 106.6 ± 8.1%, respectively, using the PSE system, and 96.8 ± 1.0% and 94.2 ± 3.9%, respectively, with the SLP-SPE system; limit of detection (LOD) and limit of quantification (LOQ) for Diuron of 0.012 mg kg-1 and 0.040 mg kg-1, respectively; LOD and LOQ for Bromacil of 0.025 mg kg-1 and 0.083 mg kg-1, respectively. The linearity used ranged from 0.04 to 1.50 mg L-1 for Diuron and from 0.08 to 1.50 mg L-1 for Bromacil. In conclusion, using the PSE system, due to high pressure and temperature, it is possible to make efficient, fast extractions with reduced solvent consumption in an inert atmosphere, which prevents sample and analyte decomposition.

Determinação de minoxidil em formulações farmacêuticas usando permanganometria

Um método clássico para a determinação de minoxidil em formulações farmacêuticas é proposto baseado na reação redox entre KMnO4 e o minoxidil. Os melhores resultados na permanganometria foram obtidos usando concentrações de 1,00 x 10-2 mol L-1 para o permanganato. O minoxidil foi usado como titulante na concentração de 2,00 x 10-2 mol L-1 diluído em solução de H2SO4 2,00 mol L-1. As recuperações para método proposto foram da ordem de 94,5 a 95,2 % dependendo da amostra comercial. O método proposto foi aplicado à amostras comerciais contendo minoxidil e comparado com resultados obtidos a partir de procedimentos cromatográficos com erros relativos da ordem de -1 a -5,26%. O procedimento se mostrou simples, rápido e pode ser uma alternativa para a determinação de minoxidil em amostras farmacêuticas, nas quais a concentração do fármaco é relativamente elevada.

Oxidative DNA damage induced by S(IV) in the presence of Cu(II) and Cu(I) complexes

The DNA damage induced by S(IV) in the presence of some Cu(II) complexes in air saturated solution was investigated. The addition of S(IV) to an air saturated solution containing CuII GGA (GGA = glycylglycyl-L-alanine), CuII G3 (G3 = triglycine) or CuII G4 (G4 = tetraglycine) and Ni(II) traces, causes rapid formation of the respective Cu(III) complex, with simultaneous O2 uptake and S(IV) oxidation. SO3•- and HO• were detected by EPR-spin trapping experiments. The DNA strand breaks were attributed to the oxysulfur radicals formed. In the reduction of Cu(II)/BCA (BCA = 4,4' dicarboxy-2-2'-biquinoline) by S(IV), with CuI BCA complex formation, there is the possible formation of carbon centered radical of BCA or peroxyl radical (ROO•) capable of oxidizing DNA bases. The intensity of DNA damage in the presence of these Cu(II) complexes and S(IV) (10-300 µmol L-1) followed the order: CuII BCA ∼ CuII G4 ∼ Cu(II) (added as Cu(NO3)2) > CuII G3 ∼ CuII GGA. Specifically for CuII BCA the damage occurred even at lower S(IV) concentration (0.1 µmol L-1). For the Cu(II) complexes with glycylglycylhistidine, glycylhistidylglycine, glycylhistidyllysine and glycylglycyltyrosylarginine the Cu(III) formation and the DNA damage was not observed.

Condições de atmosfera controlada para pêssegos "maciel" colhidos em dois estádios de maturação

O objetivo deste trabalho foi avaliar o efeito de duas temperaturas e condições de atmosfera controlada (AC) sobre a conservação de pêssegos da cultivar Maciel, colhidos em dois estádios de maturação. Os tratamentos avaliados foram: armazenamento refrigerado (AR) na temperatura de +0,5°C; AR na temperatura de -0,5°C; 2,0kPa O2 + 4,0kPa CO2 em -0,5°C; 1,0kPa O2 + 3,0kPa CO2 em -0,5°C; 2,0kPa O2 + 6,0kPa CO2 em -0,5°C. As avaliações foram realizadas após 60 dias de armazenamento e mais dois e quatro dias de exposição dos frutos à temperatura de 20ºC. Na análise realizada após dois meses de armazenamento, mais dois dias a 20°C, verificou-se que os frutos submetidos a 2,0kPa de O2 + 4,0 kPa de CO2 apresentaram maior firmeza de polpa em relação aos demais tratamentos, sendo que a mesma não foi influenciada pelo estádio de maturação. Os sólidos solúveis totais foram maiores em frutos com estádio de maturação maduro independente da condição de armazenamento. A ocorrência de podridões e escurecimento interno da polpa não foi influenciada pelo estádio de maturação. No entanto, a condição de AC de 1,0 kPa de O2 + 3,0kPa de CO2 proporcionou o menor percentual de podridões e escurecimento interno da polpa em relação aos demais tratamentos. Na avaliação realizada aos quatro dias de exposição a 20°C, os frutos colhidos no estádio maduro estavam completamente podres, independente da condição de armazenamento praticada.

Previsão de bitter pit em maçãs por meio da infiltração de Mg2+ e da aplicação de ethephon nos frutos

Estudou-se o efeito da infiltração de magnésio e cálcio no desenvolvimento de sintomas de bitter pit de maçãs 'Gala'. Examinou-se, também, a eficiência da infiltração de magnésio e da aceleração da maturação de maçãs 'Royal Gala' como métodos de previsão da ocorrência de bitter pit após o armazenamento. No primeiro experimento, maçãs 'Gala' foram infiltradas com MgCl2; CaCl2 ou MgCl2 mais CaCl2. No segundo experimento, maçãs 'Royal Gala' foram infiltradas com MgCl2; ou imersas em solução contendo ethephon por cinco minutos. Como controle, frutos de cada cultivar foram armazenados em atmosfera controlada por seis meses mais 18 dias a 20°C. Frutos infiltrados com MgCl2 apresentaram significativo acréscimo na incidência e severidade de bitter pit, proporcional à concentração de MgCl2 na solução. Frutos infiltrados com CaCl2 não apresentaram sintomas de bitter pit. A aceleração da maturação de maçãs 'Royal Gala' na colheita foi efetiva na previsão de bitter pit após o armazenamento.

Study of calcium oxalate monohydrate of kidney stones by X-ray diffraction

X-ray powder diffraction was used to study the phase composition of human renal calculi. The stones were collected from 56 donors in Vitoria, Espirito Santo state, southeastern Brazil. An XRD phase quantification revealed that 61% of the studied renal stones were composed exclusively of calcium oxalate [34% formed only by calcium oxalate rnonohydrate (COM) and 27% presents both monohydrate and dihydratate calcium oxalate]. The 39% multi-composed calculi have various other phases such as uric acid and calcium phosphate. Rietveld refinement of XRD data of one apparent monophasic (COM) renal calculus revealed the presence of a small amount of hydroxyapatite. The presence of this second phase and the morphology of the stone (ellipsoidal) indicated that this calculus can be classified as non-papillary type and its nucleation process developed in closed kidney cavities. In order to show some advantages of the X-ray powder diffraction technique, a study of the phase transformation of monohydrate calcium oxalate into calcium carbonate (CaCO(3)) was carried out by annealing of a monophasic COM calculi at 200, 300, and 400 degrees C for 48 h in a N(2) gas atmosphere. The results of the XRD for the heat treated samples is ill good agreement with the thermogravimetric analysis found in the literature and shows that X-ray powder diffraction can be used as a suitable technique to study the composition and phase diagram of renal calculi. (C) 2008 International Centre for Diffraction Data.

A SEARCH FOR FIELD HORIZONTAL-BRANCH STARS NEAR THE SOUTH GALACTIC POLE

Searches for field horizontal-branch (FHB) stars in the halo of the Galaxy in the past have been carried out by several techniques, such as objective-prism surveys and visual or infrared photometric surveys. By choosing adequate color criteria, it is possible to improve the efficiency of identifying bona fide FHB stars among the other objects that exhibit similar characteristics, such as main-sequence A-stars, blue stragglers, subdwarfs, etc. In this work, we report the results of a spectroscopic survey carried out near the south Galactic pole intended to validate FHB stars originally selected from the HK objective-prism survey of Beers and colleagues, based on near-infrared color indices. A comparison between the stellar spectra obtained in this survey with theoretical stellar atmosphere models allows us to determine T(eff), log g, and [Fe/H] for 13 stars in the sample. Stellar temperatures were calculated from measured (B-V)(o), when this measurement was available (16 stars). The color index criteria adopted in this work are shown to correctly classify 30% of the sample as FHB, 25% as non-FHB (main-sequence stars and subdwarfes), whereas 40% could not be distinguished between FHB and main-sequence stars. We compare the efficacy of different color criteria in the literature intended to select FHB stars, and discuss the use of the Mg II 4481 line to estimate the metallicity.

Genotoxic potential generated by biomass burning in the Brazilian Legal Amazon by Tradescantia micronucleus bioassay: a toxicity assessment study

Background: The Brazilian Amazon has suffered impacts from non-sustainable economic development, especially owing to the expansion of agricultural commodities into forest areas. The Tangara da Serra region, located in the southern of the Legal Amazon, is characterized by non-mechanized sugar cane production. In addition, it lies on the dispersion path of the pollution plume generated by biomass burning. The aim of this study was to assess the genotoxic potential of the atmosphere in the Tangara da Serra region, using Tradescantia pallida as in situ bioindicator. Methods: The study was conducted during the dry and rainy seasons, where the plants were exposed to two types of exposure, active and passive. Results: The results showed that in all the sampling seasons, irrespective of exposure type, there was an increase in micronucleus frequency, compared to control and that it was statistically significant in the dry season. A strong and significant relationship was also observed between the increase in micronucleus incidence and the rise in fine particulate matter, and hospital morbidity from respiratory diseases in children. Conclusions: Based on the results, we demonstrated that pollutants generated by biomass burning in the Brazilian Amazon can induce genetic damage in test plants that was more prominent during dry season, and correlated with the level of particulates and elevated respiratory morbidity.

Gene silencing during development of in vitro-produced female bovine embryos

In early development, female embryos (XX) produce twice the transcripts of X-linked genes compared with male embryos (XY). During the course of development, inactivation of the X chromosome equilibrates gene dosage, making the development of female embryos viable. Moreover, the biotechnologies used for producing embryos in vitro seem to work better with male embryos, making it easier for them to reach the blastocyst stage and allow for complete gestation. We investigated the expression of three X-linked genes that are involved in development, XIST, G6PD, and HPRT, and of the transcript interferon-tau, in male and female bovine blastocysts produced by nuclear transfer (NT) and by in vitro fertilization (IVF). Oocytes that had been matured in vitro were enucleated and reconstructed with somatic cells from adult animals at 18 h post-maturation. After fusion (two pulses of 2.25 kv/cm) and chemical activation (5.0 mu M ionomycin for 5 min and 2.0 mM 6-DMAP for 3 h), the oocytesomatic cell units were cultivated in CR2 with a monolayer of granulosa cells at 38.8 degrees C, in a humidified 5% CO(2) atmosphere. IVF embryos were inseminated, after centrifugation in a Percoll gradient, with 2 x 10(6) sperm/mL TALP medium supplemented with BSA and PHE and cultivated under the same conditions as the cloned embryos. We used real-time PCR to analyze the gene expression of individual blastocysts compared to expression of the housekeeping gene, GAPDH. The gene XIST was expressed in female embryos and not in male embryos produced by IVF, though it was expressed at low levels in male embryos produced by NT. Unlike previous reports, we found lower levels of the transcript of G6PD in females than in males, suggesting double silencing or other mechanisms of control of this gene. Female embryos produced by IVF expressed the HPRT gene at a higher level than female embryos produced by NT, suggesting that gene silencing proceeds faster in NT-produced female embryos due to ""inactivation memory"" from the nucleus donor. In conclusion, male and female embryos express different levels of X-chromosome genes and failures of these genes that are essential for development could reduce the viability of females. Nuclear transfer can modify this relation, possibly due to epigenetic memory, leading to frequent failures in nuclear reprogramming.

Observational evidences on the modulation of the South American Low Level Jet east of the Andes according the ENSO variability

The differences on the phase and wavelength of the quasi-stationary waves over the South America generated by El Nino (EN) and La Nina (LN) events seem to affect the daily evolution of the South American Low Level Jet east of the Andes (SALLJ). For the austral summer period of 1977 2004 the SALLJ episodes detected according to Bonner criterion 1 show normal to above-normal frequency in EN years, and in LN years the episodes show normal to below-normal frequency. During EN and LN years the SALLJ episodes were associated with positive rainfall anomalies over the La Plata Basin, but more intense during LN years. During EN years the increase in the SALLJ cases were associated to intensification of the Subtropical Jet (SJ) around 30 degrees S and positive Sea Level Pressure (SLP) anomalies over the western equatorial Atlantic and tropical South America, particularly over central Brazil. This favored the intensification of the northeasterly trade winds over the northern continent and it channeled by the Andes mountain to the La Plata Basin region where negative SLP are found. The SALLJ cases identified during the LN events were weaker and less frequent when compared to those for EN years. In this case the SJ was weaker than in EN years and the negative SLP anomalies over the tropical continent contributed to the inversion of the northeasterly trade winds. Also a southerly flow anomaly was generated by the geostrophic balance due to the anomalous blocking over southeast Pacific and the intense cyclonic transient over the southern tip of South America. As result the warm tropical air brought by the SALLJ encounters the cold extratropical air from the southerly winds over the La Plata basin. This configuration can increase the conditional instability over the La Plata basin and may explain the more intense positive rainfall anomalies in SALLJ cases during LN years than in EN years.

Continental passive microwave-based rainfall estimation algorithm: Application to the Amazon Basin

This paper presents a new statistical algorithm to estimate rainfall over the Amazon Basin region using the Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI). The algorithm relies on empirical relationships derived for different raining-type systems between coincident measurements of surface rainfall rate and 85-GHz polarization-corrected brightness temperature as observed by the precipitation radar (PR) and TMI on board the TRMM satellite. The scheme includes rain/no-rain area delineation (screening) and system-type classification routines for rain retrieval. The algorithm is validated against independent measurements of the TRMM-PR and S-band dual-polarization Doppler radar (S-Pol) surface rainfall data for two different periods. Moreover, the performance of this rainfall estimation technique is evaluated against well-known methods, namely, the TRMM-2A12 [ the Goddard profiling algorithm (GPROF)], the Goddard scattering algorithm (GSCAT), and the National Environmental Satellite, Data, and Information Service (NESDIS) algorithms. The proposed algorithm shows a normalized bias of approximately 23% for both PR and S-Pol ground truth datasets and a mean error of 0.244 mm h(-1) ( PR) and -0.157 mm h(-1)(S-Pol). For rain volume estimates using PR as reference, a correlation coefficient of 0.939 and a normalized bias of 0.039 were found. With respect to rainfall distributions and rain area comparisons, the results showed that the formulation proposed is efficient and compatible with the physics and dynamics of the observed systems over the area of interest. The performance of the other algorithms showed that GSCAT presented low normalized bias for rain areas and rain volume [0.346 ( PR) and 0.361 (S-Pol)], and GPROF showed rainfall distribution similar to that of the PR and S-Pol but with a bimodal distribution. Last, the five algorithms were evaluated during the TRMM-Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA) 1999 field campaign to verify the precipitation characteristics observed during the easterly and westerly Amazon wind flow regimes. The proposed algorithm presented a cumulative rainfall distribution similar to the observations during the easterly regime, but it underestimated for the westerly period for rainfall rates above 5 mm h(-1). NESDIS(1) overestimated for both wind regimes but presented the best westerly representation. NESDIS(2), GSCAT, and GPROF underestimated in both regimes, but GPROF was closer to the observations during the easterly flow.

The role of the observed tropical convection in the generation of frost events in the southern cone of South America

Based on previous results obtained from observations and linear wave theory analysis, the hypothesis that large-scale patterns can generate extreme cold events in southeast South America through the propagation of remotely excited Rossby waves was already suggested. This work will confirm these findings and extend their analysis through a series of numerical experiments using a primitive equation model where waves are excited by a thermal forcing situated in positions chosen according to observed convection anomalies over the equatorial region. The basic state used for these experiments is a composite of austral winters with maximum and minimum frequency of occurrence of generalized frosts that can affect a large area known as the Wet Pampas located in the central and eastern part of Argentina. The results suggest that stationary Rossby waves may be one important mechanism linking anomalous tropical convection with the extreme cold events in the Wet Pampas. The combination of tropical convection and a specific basic state can generate the right environment to guide the Rossby waves trigged by the tropical forcing towards South America. Depending on the phase of the waves entering the South American continent, they can favour the advection of anomalous wind at low levels from the south carrying cold and dry air over the whole southern extreme of the continent, producing a generalized frost in the Wet Pampa region. On the other hand, when a basic state based on the composites of minimum frosts is used, an anomalous anticyclone over the southern part of the continent generates a circulation with a south-southeast wind which brings maritime air and therefore humidity over the Wet Pampas region, creating negative temperature anomalies only over the northeastern part of the region. Under these conditions even if frosts occur they would not be generalized, as observed for the other basic state with maximum frequency of occurrence of generalized frosts.

First stars XI. Chemical composition of the extremely metal-poor dwarfs in the binary CS 22876-032

Context. Unevolved metal-poor stars constitute a fossil record of the early Galaxy, and can provide invaluable information on the properties of the first generations of stars. Binary systems also provide direct information on the stellar masses of their member stars. Aims. The purpose of this investigation is a detailed abundance study of the double-lined spectroscopic binary CS 22876-032, which comprises the two most metal-poor dwarfs known. Methods. We used high-resolution, high-S/N ratio spectra from the UVES spectrograph at the ESO VLT telescope. Long-term radial-velocity measurements and broad-band photometry allowed us to determine improved orbital elements and stellar parameters for both components. We used OSMARCS 1D models and the TURBOSPECTRUM spectral synthesis code to determine the abundances of Li, O, Na, Mg, Al, Si, Ca, Sc, Ti, Cr, Mn, Fe, Co and Ni. We also used the (COBOLD)-B-5 model atmosphere code to compute the 3D abundance corrections, notably for Li and O. Results. We find a metallicity of [Fe/H] similar to -3.6 for both stars, using 1D models with 3D corrections of similar to -0.1 dex from averaged 3D models. We determine the oxygen abundance from the near-UV OH bands; the 3D corrections are large, -1 and -1.5 dex for the secondary and primary respectively, and yield [O/Fe] similar to 0.8, close to the high-quality results obtained from the [OI] 630 nm line in metal-poor giants. Other [alpha/Fe] ratios are consistent with those measured in other dwarfs and giants with similar [Fe/H], although Ca and Si are somewhat low ([X/Fe] less than or similar to 0). Other element ratios follow those of other halo stars. The Li abundance of the primary star is consistent with the Spite plateau, but the secondary shows a lower abundance; 3D corrections are small. Conclusions. The Li abundance in the primary star supports the extension of the Spite Plateau value at the lowest metallicities, without any decrease. The low abundance in the secondary star could be explained by endogenic Li depletion, due to its cooler temperature. If this is not the case, another, yet unknown mechanism may be causing increased scatter in A( Li) at the lowest metallicities.

Transiting exoplanets from the CoRoT space mission XVIII. CoRoT-18b: a massive hot Jupiter on a prograde, nearly aligned orbit

We report the detection of CoRoT-18b, a massive hot Jupiter transiting in front of its host star with a period of 1.9000693 +/- 0.0000028 days. This planet was discovered thanks to photometric data secured with the CoRoT satellite combined with spectroscopic and photometric ground-based follow-up observations. The planet has a mass M(p) = 3.47 +/- 0.38 M(Jup), a radius R(p) = 1.31 +/- 0.18 R(Jup), and a density rho(p) = 2.2 +/- 0.8 g cm(-3). It orbits a G9V star with a mass M(*) = 0.95 +/- 0.15 M(circle dot), a radius R(*) = 1.00 +/- 0.13 R(circle dot), and a rotation period P(rot) = 5.4 +/- 0.4 days. The age of the system remains uncertain, with stellar evolution models pointing either to a few tens Ma or several Ga, while gyrochronology and lithium abundance point towards ages of a few hundred Ma. This mismatch potentially points to a problem in our understanding of the evolution of young stars, with possibly significant implications for stellar physics and the interpretation of inferred sizes of exoplanets around young stars. We detected the RossiterMcLaughlin anomaly in the CoRoT-18 system thanks to the spectroscopic observation of a transit. We measured the obliquity psi = 20 degrees +/- 20 degrees +/- (sky-projected value lambda = -10 degrees +/- 20 degrees), indicating that the planet orbits in the same way as the star is rotating and that this prograde orbit is nearly aligned with the stellar equator.

THE SPECTRAL EVOLUTION AND EJECTA OF RECURRENT NOVA U Sco IN THE 2010 OUTBURST

Synoptic spectroscopic observations of the U Sco 2010 outburst from maximum light to quiescence as well as a contemporaneous X-ray observation are presented and analyzed. The X-ray spectrum 52 days after outburst indicates a hot source ( kT(bb) similar to 70 eV). Narrow-line components from the irradiated companion atmosphere were observed in hydrogen and helium optical recombination lines. The formation of a nebular spectrum is seen for the first time in this class of recurrent novae, allowing a detailed study of the ejecta using photoionization models. Unusual [O III] auroral-to-nebular line ratios were found and possible scenarios of their origin are discussed. The modeling of the emission line spectrum suggests highly heterogeneous ejecta with masses around or above 3 x 10(-6) M(sun).