Optimisation of stir bar sorptive extraction and liquid desorption combined with large volume injection-gas chromatography–quadrupole mass spectrometry for the determination of volatile compounds in wines

Stir bar sorptive extraction and liquid desorption followed by large volume injection coupled to gas chromatography–quadrupole mass spectrometry (SBSE–LD/LVI-GC–qMS) had been applied for the determination of volatiles in wines. The methodology was optimised in terms of extraction time and influence of ethanol in the matrix; LD conditions, and instrumental settings. The optimisation was carried out by using 10 standards representative of the main chemical families of wine, i.e. guaiazulene, E,E-farnesol, β-ionone, geranylacetone, ethyl decanoate, β-citronellol, 2-phenylethanol, linalool, hexyl acetate and hexanol. The methodology shows good linearity over the concentration range tested, with correlation coefficients higher than 0.9821, a good reproducibility was attained (8.9–17.8%), and low detection limits were achieved for nine volatile compounds (0.05–9.09 μg L−1), with the exception of 2-phenylethanol due to low recovery by SBSE. The analytical ability of the SBSE–LD/LVI-GC–qMS methodology was tested in real matrices, such as sparkling and table wines using analytical curves prepared by using the 10 standards where each one was applied to quantify the structurally related compounds. This methodology allowed, in a single run, the quantification of 67 wine volatiles at levels lower than their respective olfactory thresholds. The proposed methodology demonstrated to be easy to work-up, reliable, sensitive and with low sample requirement to monitor the volatile fraction of wine.

Novas fronteiras petrolíferas no Brasil : uma análise da necessidade de nova regulamentação da área do pré-sal sob a ótica constitucional

The Oil industry in Brazil has gone through several stages during the economical, political and social historical process. However, the significative changes have happened in the last fifteen years, due to market opening arising from the relaxation of the state monopoly over the Oil deposits and its derivatives. The edition of the Constitutional Amendment #9, changing the first paragraph of the 177th item of the Federal Constitution, marked the end of a stiffness about the monopoly that the Brazilian state kept in relation to the exploration and research of Oil and Gas. The economical order was fundamental to actualize the idea contained in the #9 Amendment, since its contents has the power to set up measures to be adopted by public power in order to organize the economical relations from a social viewpoint. The new brazilian Oil scenery, called pre-salt, presents itself in a way to amaze the economical markets, in addition to creating a new perspective to the social sector. This work will identify, in this new scenario, the need for change in the legal system. Nevertheless, this subject must not be treated in a thoughtless way: being an exhaustible good, we shall not forget that the future generations also must benefit from the exploration of natural resources recently discovered. The settlement of a new regulatory mark, including the change in the concession contract model to production and sharing is one of the suggested solutions as a bill in the National Congress, in an attempt to ensure the sovereignty of the nation. The constitutionality of a new regulatory mark is questioned, starting from an analysis of the state monopoly, grounding the comprehnsions in the brazilian constitutions, the relevance of the creation of Petrobras for self-assertion of the state about the monopoly of Oil and derivatives, and its posture after the Constitutional Amendment nº 9 (1995), when a company stops having control of the state monopoly, beginning to compete in a fairly way with other companies. The market opening and private initiative are emphasized from the viewpoint of the Constitutional Principles of the Economical and Social Order. The relaxation of the monopoly regarding the exploratory activity in the Federal Constitution doesn't deprive from the Union the ownerships of underground goods, enabling to this federal entity to contract, directly or by concession of exploration of goods, to state-owned or private companies. The existing oil in the pre-salt layer transforms the scenario from very high risk to low risk, which gives the Union the possibility of defining another way of exploring this resources in the best interests of the Public Administration

Does ISO 14001 work in Brazil?

As a result of increasing global awareness about the importance of the environment, depletion of natural resources and legal pressures for companies to manage their processes in a sustainable manner, ISO 14001 systems have been gaining increasingly more importance in the organizational scenario. These elements are even more critical in emerging nations due to less awareness and fewer demands by governments and the population in relation to environmental issues. Therefore, the main objective of this study is to verify the benefits and difficulties of Environmental Management Systems based on ISO 14001 at industries in the state of São Paulo - Brazil (an emerging country) by conducting a survey to subsidize the proposal for actions in the public, academic and private sectors to promote the use of this standard of reference and strengthen its results in Brazil. A questionnaire was sent to 194 companies from the National Institute of Metrology, Standardization and Industrial Quality database. 69 answered, representing a return rate of 35.36%. The main benefits identified are related to the development of preventive environmental actions, reduction in the consumption of power, water, gas and fuel oil, and a positive influence on other internal management processes. The main difficulties are related to cost increases from ISO 14001 management systems and the constant changes in environmental legislation in Brazil. Some actions are proposed at the end of the analyses to intensify the use and improve the results of this standard, such as changes in government legislation and its collective development and implementation in industries. (C) 2010 Elsevier Ltd. All rights reserved.

Comparação entre metodologias de extração de HPAs em água utilizando um planejamento fatorial com quantificação no CG/EM

PAHs (Polycyclic Aromatic Hydrocarbons) are a group of organic substances which receive considerable attention because of the carcinogenic and mutagenic properties of some of them. It is therefore important to determine the PAHs in different environmental matrices. Several studies have shown the use of gas chromatography coupled to mass spectrometry as a technique for quantification of PAHs by presenting excellent detection limits. This study aimed to develop an analytical methodology for the determination of 16 PAHs listed by the USEPA, test two methods for extraction of PAHs in water from a 23 factorial design, quantify them through the analytical technique coupled to gas chromatography mass spectrometry (GC/MS) using the method developed, and finally apply the results in chemometrics. The sample was synthesized and subjected to tests of the 23 factorial design, which has the factors: the type of extraction technique (ultrasound and digester), the ratio solvent / sample (1:1 and 1:3) and the type of solvent (dichloromethane / hexane and acetone / dichloromethane). The responses of eight combinations of the factorial design were obtained from the quantification by external calibration in GC/MS. The quantification method was developed from an optimized adaptation of the USEPA Method 8270. We used the full scan mode as a way of acquiring the mass spectra of 16 PAHs. The time in which the samples were subjected to ultrasound was fixed at 10 min and held an investigation to establish the conditions of power and time in the digester. We had the best response in the investigation of the digester power of 100 watts and the time of six minutes. The factorial design of liquid-liquid extraction showed that the most representative factors were: the use of the digester as extraction technique, the ratio solvent / sample 1:1 and the use of a 1:1 mixture of dichloromethane / hexane as a solvent more suitable. These results showed that the 1:1 mixture of dichloromethane / hexane is an excellent mixture to recover the extraction of PAHs an aqueous sample using the microwave digester. The optimization of the method of separation, identification and quantification of PAHs in the GC/MS was valid for 16 PAHs present in each chromatogram of the samples

Differential responses between mature and young leaves of sunflower plants to oxidative stress caused by water deficit

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

Nebular gas drag and co-orbital system dynamics

Aims. We study trajectories of planetesimals whose orbits decay due to gas drag in a primordial solar nebula and are perturbed by the gravity of the secondary body on an eccentric orbit whose mass ratio takes values from mu(2) = 10(-7) to mu(2) = 10(-3) increasing ten times at each step. Each planetesimal ultimately suffers one of the three possible fates: (1) trapping in a mean motion resonance with the secondary body; (2) collision with the secondary body and consequent increase of its mass; or (3) diffusion after crossing the orbit of the secondary body.Methods. We take the Burlirsh-Stoer numerical algorithm in order to integrate the Newtonian equations of the planar, elliptical restricted three-body problem with the secondary body and the planetesimal orbiting the primary. It is assumed that there is no interaction among planetesimals, and also that the gas does not affect the orbit of the secondary body.Results. The results show that the optimal value of the gas drag constant k for the 1: 1 resonance is between 0.9 and 1.25, representing a meter size planetesimal for each AU of orbital radius. In this study, the conditions of the gas drag are such that in theory, L4 no longer exists in the circular case for a critical value of k that defines a limit size of the planetesimal, but for a secondary body with an eccentricity larger than 0.05 when mu(2) = 10(-6), it reappears. The decrease of the cutoff collision radius increase the difusions but does not affect the distribution of trapping. The contribution to the mass accretion of the secondary body is over 40% with a collision radius 0.05R(Hill) and less than 15% with 0.005R(Hill) for mu(2) = 10(-7). The trappings no longer occur when the drag constant k reachs 30. That means that the size limit of planetesimal trapping is 0.2 m per AU of orbital radius. In most cases, this accretion occurs for a weak gas drag and small secondary eccentricity. The diffusions represent most of the simulations showing that gas drag is an efficient process in scattering planetesimals and that the trapping of planetesimals in the 1: 1 resonance is a less probable fate. These results depend on the specific drag force chosen.

Antioxidant therapy to prevent preeclampsia - A Randomized controlled trial

OBJECTIVE: To study whether antioxidant supplementation will reduce the incidence of preeclampsia among patients at increased risk.METHODS: A randomized, placebo-controlled, double-blind clinical trial was conducted at four Brazilian sites. Women between 12 0/7 weeks and 19 6/7 weeks of gestation and diagnosed to have chronic hypertension or a prior history of preeclampsia were randomly assigned to daily treatment with both vitamin C (1,000 mg) and vitamin E (400 International Units) or placebo. Analyses were adjusted for clinical site and risk group (prior preeclampsia, chronic hypertension, or both). A sample size of 734 would provide 80% power to detect a 40% reduction in the risk of preeclampsia, assuming a placebo group rate of 21% and alpha=.05. The a level for the final analysis, adjusted for interim looks, was 0.0458.RESULTS: Outcome data for 707 of 739 randomly assigned patients revealed no significant reduction in the rate of preeclampsia (study drug, 13.8% [49 of 355] compared with placebo, 15.6% [55 of 352], adjusted risk ratio 0.87 [95.42% confidence interval 0.61-1.25]). There were no differences in mean gestational age at delivery or rates of perinatal mortality, abruptio placentae, pre-term delivery, and small for gestational age or low birth weight infants. Among patients without chronic hypertension, there was a slightly higher rate of severe preeclampsia in the study group (study drug, 6.5% [11 of 170] compared with placebo, 2.4% [4 of 168], exact P=.11, odds ratio 2.78, 95% confidence interval 0.79-12.62).CONCLUSION: This trial failed to demonstrate a benefit of antioxidant supplementation in reducing the rate of preeclampsia among'patients with chronic hypertension and/or prior preeclampsia.

Evaluation of in vitro gas production of roughages and their mixtures using the curves subtraction method

The in vitro gas production of four single roughages and their paired combinations (1:1 on dry matter basis) were evaluated. Two roughage samples (100 mg) per treatment were fermented with ruminal fluid during a 48 h incubation period. Total 48 h gas volumes of fermentation dry matter (DM), neutral detergent fiber (NDF) and soluble compounds in neutral detergent (NDS) were for sugarcane = 16.8, 11.2, 6.9 mL; sugarcane + corn silage = 20.1, 12.6, 9.1 mL; sugarcane + 60-day elephantgrass = 16.5, 17.6 mL; sugarcane + 180-day elephantgrass = 13.8, 8.2, 5.9 mL; corn silage = 18.8, 16.8, 4.7 mL; corn silage + 60-day elephantgrass = 16.3, 15.4, 2.4 mL; corn silage + 180-day elephantgrass = 16.1, 11.8, 4.2 mL; 60-day elephantgrass = 16.9, 19.0 mL and 180-day elephantgrass = fermented 10.7, 12.2 mL, respectively. The NDS gas production was not possible to estimate for sugarcane + 60-day elephantgrass, 60-day elephantgrass and 180-day elephantgrass. The present data shows that the curves subtraction method can be an option to evaluate the contribution of the soluble fractions in roughages to digestion kinetics. However, this method underestimates the NDS gas contribution when roughages are low in crude protein and soluble carbohydrates. It is advisable to directly apply the two-compartmental mathematical model to the digestion curves for roughage DM, when determining the NDS gas volume and the digestion rate. This method is more straightforward and accurate when compared to the curve subtraction method. Non-structural carbohydrates combined with fiber and protein promoted a positive associative effect in sugarcane + corn silage (50:50) mixture. Therefore, it can be concluded that the soluble fraction of roughages greatly contributes to gas production. (C) 2004 Elsevier B.V. All rights reserved.

Resolving power of 2D pion interferometry

A χ2 analysis is performed to test the resolving power of two-dimensional pion interferometry using for illustration the preliminary E802 data on Si+Au at 14.6 A GeV/c. We find that the resolving power to distinguish two decoupling geometries of different dynamical models is enhanced by studying the variation of the mean χ2 per degrees of freedom with respect to the range of the analysis in the qT, qL plane. The preliminary data seem to rule out dynamical models with significant ω, η resonance formation yields.

Determination of acetonitrile and cyanide in rat blood: Application to an experimental study

Methods were developed for the analysis of acetonitrile and its metabolite cyanide in the blood of rats exposed to acetonitrile. Acetonitrile was analyzed by the headspace technique coupled to gas chromatography with detection by flame ionization, and cyanide was analyzed by high-performance liquid chromatography with fluorescence detection (λ ex = 418 nm and λ em = 460 nm) after derivatization of the ion with naphthalene 2,3-dicarboxyaldehyde and taurine. The quantitation limits of the methods for the analysis of acetonitrile and cyanide were 4.875 μg/mL and 0.025 μg/mL, respectively. The coefficients of variation of 10% or less obtained for intra- and interassay precision indicate the precision of these analytical methods and the systematic errors, all less than 5%, indicate that the methods are quite accurate. The methods were applied to an experimental study after the animals received acetonitrile at the doses of 2 mmol/kg or 5 mmol/kg.

Energia de briquetes produzidos com rejeitos de resíduos sólidos urbanos e madeira de Eucalyptus grandis

The incentive for consumption and production in large quantity in modern society generates enormous amounts of urban solid residues in the form of municipal solid waste (MSW). With the intention of reducing these residues of the municipal waste tips and to generate energy, briquettes with mixtures of MSW and residues of Eucalyptus grandis were produced. The briquettes were manufactured with 0, 5, 10, 15, 20 and 25% of MSW in the mixture with wood waste and 12% of moisture content. The analyzed parameters used to choose the best treatments were combustion analysis versus ash content, mechanical strength and energy content. The briquettes up to 10% of MSW showed low resistance, and above 15% showed large increase in ash content. Therefore, the treatment that fulfilled the requirements for combustion versus ash content and mechanical resistance was of at least 15% of MSW, since the source of the ash is unidentified. Considering the net energy content, the best treatment was 25% of MSW, with 17,175 kJ kg-1. Nevertheless, it is strongly advised that further studies related to gas emissions are necessary.

Análise de sistemas de cogeração com gaseificação de licor negro no setor de papel e celulose

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Switch allocation problems in power distribution systems

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Impaired lung function in individuals chronically exposed to biomass combustion

Background: The use of biomass for cooking and heating is considered an important factor associated with respiratory diseases. However, few studies evaluate the amount of particulate matter less than 2.5 mu in diameter (PM2.5), symptoms and lung function in the same population. Objectives: To evaluate the respiratory effects of biomass combustion and compare the results with those of individuals from the same community in Brazil using liquefied petroleum gas (Gas). Methods: 1402 individuals in 260 residences were divided into three groups according to exposure (Gas, Indoor-Biomass, Outside-Biomass). Respiratory symptoms were assessed using questionnaires. Reflectance of paper filters was used to assess particulate matter exposure. In 48 residences the amount of PM2.5 was also quantified. Pulmonary function tests were performed in 120 individuals. Results: Reflectance index correlated directly with PM2.5 (r=0.92) and was used to estimate exposure (ePM2.5). There was a significant increase in ePM2.5 in Indoor-Biomass and Outside-Biomass, compared to Gas. There was a significantly increased odds ratio (OR) for cough, wheezing and dyspnea in adults exposed to Indoor-Biomass (OR=2.93, 2.33, 2.59, respectively) and Outside-Biomass (OR=1.78, 1.78, 1.80, respectively) compared to Gas. Pulmonary function tests revealed both Non-Smoker-Biomass and Smoker-Gas individuals to have decreased %predicted-forced expiratory volume in the first second (FEV1) and FEV1/forced vital capacity (FVC) as compared to Non-Smoker-Gas. Pulmonary function tests data was inversely correlated with duration and ePM2.5. The prevalence of airway obstruction was 20% in both Non-Smoker-Biomass and Smoker-Gas subjects. Conclusion: Chronic exposure to biomass combustion is associated with increased prevalence of respiratory symptoms, reduced lung function and development of chronic obstructive pulmonary disease. These effects are associated with the duration and magnitude of exposure and are exacerbated by tobacco smoke. (C) 2011 Elsevier Inc. All rights reserved.

Source of slow lithium atoms from Ne or H-2 matrix isolation sublimation

We have studied, via laser absorption spectroscopy, the velocity distribution of Li-7 atoms released from cryogenic matrices of solid neon or molecular hydrogen. The Li atoms are implanted into the Ne or H-2 matrices - grown onto a sapphire substrate - by laser ablation of a solid Li or LiH precursor. A heat pulse is then applied to the sapphire substrate sublimating the matrix together with the isolated atoms. With a NiCr film resistor deposited directly onto the sapphire substrate we are able to transfer high instantaneous power to the matrix, thus reaching a fast sublimation regime. In this regime the Li atoms can get entrained in the released matrix gas, and we were also able to achieve matrix sublimation times down to 10 mu s for both H-2 or Ne matrix, enabling us to proceed with the trapping of the species of our interest such as atomic hydrogen, lithium, and molecules. The sublimation of the H-2 matrix, with its large center-of-mass velocity, provides evidence for a new regime of one-dimensional thermalization. The laser ablated Li seems to penetrate the H-2 matrix deeper than it does in Ne. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4704125]