HPLC-DAD methodology for the quantification of organic acids, furans and polyphenols by direct injection of wine samples

This article proposes a simple and sensitive HPLC method with photo-diode array detection for the analysis of organic acids, monomeric polyphenols and furanic compounds in wine samples by direct injection. The chromatographic separation of 8 organic acids, 2 furans and 22 phenolic compounds was carried out with a buffered solution (pH 2.70) and acetonitrile as mobile phases and a difunctionally bonded C18 stationary phase, Atlantis dC18 (250 4.6 mm, 5mm) column. The elution was performed in 12 min for the organic acids and in 60 min for the phenolic compounds, including phenolic acids, stilbenes and flavonoids. Target compounds were detected at 210 nm (organic acids, flavan-3-ols and benzoic acids), 254 nm (ellagic acid), 280 nm (furans and cinnamic acid), 315 nm (hydroxycinnamic acids and trans-resveratrol) and 360 nm (flavonoids). The RSD for the repeatability test (n55) of peak area and retention times were below 3.1 and 0.3%, respectively, for phenolics and below 1.0 and 0.2% for organic acids. The RSDs expressing the reproducibility of the method were higher than for the repeatability results but all below 9.0%. Method accuracy was evaluated by the recovery results, with averaged values between 80 and 104% for polyphenols and 97–105% for organic acids. The calibration curves, obtained by triplicate injection of standard solutions, showed good linearity with regression coefficients higher than 0.9982 for polyphenols and 0.9997 for organic acids. The LOD was in the range of 0.07–0.49 mg/L for polyphenols (cinnamic and gallic acids, respectively) and 0.001–0.046 g/L for organic acids (oxalic and lactic acids, respectively). The method was successfully used to measure and assess the polyphenolic fingerprint and organic acids profile of red, white, rose ´ and fortified wines.

A sensitive microextraction by packed sorbent-based methodology combined with ultra-high pressure liquid chromatography as a powerful technique for analysis of biologically active flavonols in wines

A new approach based on microextraction by packed sorbent (MEPS) and reversed-phase high-throughput ultra high pressure liquid chromatography (UHPLC) method that uses a gradient elution and diode array detection to quantitate three biologically active flavonols in wines, myricetin, quercetin, and kaempferol, is described. In addition to performing routine experiments to establish the validity of the assay to internationally accepted criteria (selectivity, linearity, sensitivity, precision, accuracy), experiments are included to assess the effect of the important experimental parameters such as the type of sorbent material (C2, C8, C18, SIL, and C8/SCX), number of extraction cycles (extract-discard), elution volume, sample volume, and ethanol content, on the MEPS performance. The optimal conditions of MEPS extraction were obtained using C8 sorbent and small sample volumes (250 μL) in five extraction cycle and in a short time period (about 5 min for the entire sample preparation step). Under optimized conditions, excellent linearity View the MathML source(Rvalues2>0.9963), limits of detection of 0.006 μg mL−1 (quercetin) to 0.013 μg mL−1 (myricetin) and precision within 0.5–3.1% were observed for the target flavonols. The average recoveries of myricetin, quercetin and kaempferol for real samples were 83.0–97.7% with relative standard deviation (RSD, %) lower than 1.6%. The results obtained showed that the most abundant flavonol in the analyzed samples was myricetin (5.8 ± 3.7 μg mL−1). Quercetin (0.97 ± 0.41 μg mL−1) and kaempferol (0.66 ± 0.24 μg mL−1) were found in a lower concentration. The optimized MEPSC8 method was compared with a reverse-phase solid-phase extraction (SPE) procedure using as sorbent a macroporous copolymer made from a balanced ratio of two monomers, the lipophilic divinylbenzene and the hydrophilic N-vinylpyrrolidone (Oasis HLB) were used as reference. MEPSC8 approach offers an attractive alternative for analysis of flavonols in wines, providing a number of advantages including highest extraction efficiency (from 85.9 ± 0.9% to 92.1 ± 0.5%) in the shortest extraction time with low solvent consumption, fast sample throughput, more environmentally friendly and easy to perform.

Modelagem dinâmica e simulação computacional de poços de petróleo verticais e direcionais com elevação por bombeio mecânico

LINS, Filipe C. A. et al. Modelagem dinâmica e simulação computacional de poços de petróleo verticais e direcionais com elevação por bombeio mecânico. In: CONGRESSO BRASILEIRO DE PESQUISA E DESENVOLVIMENTO EM PETRÓLEO E GÁS, 5. 2009, Fortaleza, CE. Anais... Fortaleza: CBPDPetro, 2009.

Formulação de grautes leves para a cimentação de poços de petróleo onshore

Grautes are dry mixes with hydraulic characteristics widely used in construction. This material comprises cement, mineral additives and dosed in accordance with the desired properties. The use of grautes in cementing oil wells potentially increases the precision in the composition of the mixture, since it is requires only the addition of the mixing water before its pumping. Such benefit may be availed in cementing wells since the formulations grautes meet the temperature and pressure characteristics typical of wells. The objective of this study is to evaluate the effect of adding different percentages of industrial minerals properties of light grautes for onshore oil wells. For the formulation of the employees were grautes light industrial minerals and waste minerals abundant in the Northeast, in addiction to Portland cement and chemical additives Special class. Grautes were formulated with densities between 1.55 g/cm3 (13.0 lb/gal) and 1.68 g/cm3 (14 lb/gal). Tests results showed that grautes with higher density in the range studied meet the specifications for cementation of shallow wells onshore. The compositions lighter can also be adjusted for applying the material in the cementation of oil wells

Avaliação da adição de Nanosílica e silicato de sódio em pastas de cimento para poços de petróleo com baixo gradiente de fratura

The oil wells cementing is a critical step during the phase of well drilling, because problems during the operation of slurry pumping and an incomplete filling of the annular space between the metal casing and the formation can cause the slurry loss. Therefore, the slurry adopted in primary cementing an oil well must be properly dosed so that these problems are avoided during its pumping. When you drill a well in a weak rock formation requires even more careful, because should be a limit of hydrostatic pressure exerted during cementation, that does not occur rock collapse. With the objective of performing the cementing of a well whose formation is weak or unconsolidated are employed lighter slurries. Thus, this study used slurries with sodium silicate and nano silica in concentrations of 0,1; 0,4; 0,7 e 1,0 gpc, in which the slurries with nano silica showed the rheological parameters higher concentrations of up to 0.7 gpc and for concentration of 1.0 the slurry with sodium silicate obtained the highest values, remaining above the limits for application in fields, mainly wells with low fracture gradient, because a significant increase in viscosity may result in an increase in pressure pumping in operations of secondary cementations. Furthermore, there was no decrease in strength with increasing concentration of additive. Then, it is possible use of these additives to formulate Lighter slurry

Modelagem e simulação de um sistema de bombeio mecânico em poços direcionais utilizando parâmetros concentrados

This work aims presenting the development of a model and computer simulation of a sucker rod pumping system. This system take into account the well geometry, the flow through the tubing, the dynamic behavior of the rod string and the use of a induction motor model. The rod string were modeled using concentrated parameters, allowing the use of ordinary differential equations systems to simulate it s behavior

Ambiente para avaliação de controladores fuzzy aplicados ao método de elevação artificial por bombeio centrífugo submerso

From their early days, Electrical Submergible Pumping (ESP) units have excelled in lifting much greater liquid rates than most of the other types of artificial lift and developed by good performance in wells with high BSW, in onshore and offshore environments. For all artificial lift system, the lifetime and frequency of interventions are of paramount importance, given the high costs of rigs and equipment, plus the losses coming from a halt in production. In search of a better life of the system comes the need to work with the same efficiency and security within the limits of their equipment, this implies the need for periodic adjustments, monitoring and control. How is increasing the prospect of minimizing direct human actions, these adjustments should be made increasingly via automation. The automated system not only provides a longer life, but also greater control over the production of the well. The controller is the brain of most automation systems, it is inserted the logic and strategies in the work process in order to get you to work efficiently. So great is the importance of controlling for any automation system is expected that, with better understanding of ESP system and the development of research, many controllers will be proposed for this method of artificial lift. Once a controller is proposed, it must be tested and validated before they take it as efficient and functional. The use of a producing well or a test well could favor the completion of testing, but with the serious risk that flaws in the design of the controller were to cause damage to oil well equipment, many of them expensive. Given this reality, the main objective of the present work is to present an environment for evaluation of fuzzy controllers for wells equipped with ESP system, using a computer simulator representing a virtual oil well, a software design fuzzy controllers and a PLC. The use of the proposed environment will enable a reduction in time required for testing and adjustments to the controller and evaluated a rapid diagnosis of their efficiency and effectiveness. The control algorithms are implemented in both high-level language, through the controller design software, such as specific language for programming PLCs, Ladder Diagram language.

Avaliação da correlação entre os parâmetros, carbono orgânico total e elementos tóxicos, em solo de um posto de serviço e revenda de combustíveis

Today a major responsibility for the contamination of soil and groundwater and surface water are establishments known as gas stations of fuel which has attracted increasing attention from both the general population as the state agencies of environmental control due to leaks in storage tanks and mainly to disruption of pipe corrosion of tanks and pumping. Other services, like oil changes and car wash are also causes for concern in this type of establishment. These leaks can cause or waste produced, and the contamination of aquifers, serious health problems and public safety, since most of these stations located in urban areas. Based on this, the work was to evaluate soil contamination of a particular service station and fuel sales in the city of Natal, through the quantification of heavy metals like Cd, Cu, Cr, Ni, Pb, Zn of total organic carbon (TOC) and organic matter using different techniques such as optical emission spectrometry with inductively coupled plasma source (ICP OES), Total Organic Carbon analyzer and gravimetric analysis respectively. And also to characterize the soil through particle size analysis. Samples were taken in 21 georeferenced points and collected in the same period. The soils sampled in sampling stations P3, P5, P6, P10, P11, P12, P13, P14, P15, P17, P18 and P20 showed the smallest size fractions ranging from fine sand to medium sand. The other study sites ranged from fine sand to medium sand, except the point P8 showed that only the type size medium sand and P19, indicating a particle size of the coarse type. The small correlation of organic matter with the elements studied in this work suggests that these are not of anthropogenic origin but geochemical support

Nova técnica para obtenção de fraturas com altíssima condutividade em poços de petróleo

Increase hydrocarbons production is the main goal of the oilwell industry worldwide. Hydraulic fracturing is often applied to achieve this goal due to a combination of attractive aspects including easiness and low operational costs associated with fast and highly economical response. Conventional fracturing usually involves high-flowing high-pressure pumping of a viscous fluid responsible for opening the fracture in the hydrocarbon producing rock. The thickness of the fracture should be enough to assure the penetration of the particles of a solid proppant into the rock. The proppant is driven into the target formation by a carrier fluid. After pumping, all fluids are filtered through the faces of the fracture and penetrate the rock. The proppant remains in the fracture holding it open and assuring high hydraulic conductivity. The present study proposes a different approach for hydraulic fracturing. Fractures with infinity conductivity are formed and used to further improve the production of highly permeable formations as well as to produce long fractures in naturally fractured formations. Naturally open fractures with infinite conductivity are usually encountered. They can be observed in rock outcrops and core plugs, or noticed by the total loss of circulation during drilling (even with low density fluids), image profiles, pumping tests (Mini-Frac and Mini Fall Off), and injection tests below fracturing pressure, whose flow is higher than expected for radial Darcian ones. Naturally occurring fractures are kept open by randomly shaped and placed supporting points, able to hold the faces of the fracture separate even under typical closing pressures. The approach presented herein generates infinite conductivity canal held open by artificially created parallel supporting areas positioned both horizontally and vertically. The size of these areas is designed to hold the permeable zones open supported by the impermeable areas. The England & Green equation was used to theoretically prove that the fracture can be held open by such artificially created set of horizontal parallel supporting areas. To assess the benefits of fractures characterized by infinite conductivity, an overall comparison with finite conductivity fractures was carried out using a series of parameters including fracture pressure loss and dimensionless conductivity as a function of flow production, FOI folds of increase, flow production and cumulative production as a function of time, and finally plots of net present value and productivity index

Simulação do escoamento monofásico em um estágio de uma bomba centrífuga utilizando técnicas de fluidodinâmica computacional

Oil production and exploration techniques have evolved in the last decades in order to increase fluid flows and optimize how the required equipment are used. The base functioning of Electric Submersible Pumping (ESP) lift method is the use of an electric downhole motor to move a centrifugal pump and transport the fluids to the surface. The Electric Submersible Pumping is an option that has been gaining ground among the methods of Artificial Lift due to the ability to handle a large flow of liquid in onshore and offshore environments. The performance of a well equipped with ESP systems is intrinsically related to the centrifugal pump operation. It is the pump that has the function to turn the motor power into Head. In this present work, a computer model to analyze the three-dimensional flow in a centrifugal pump used in Electric Submersible Pumping has been developed. Through the commercial program, ANSYS® CFX®, initially using water as fluid flow, the geometry and simulation parameters have been defined in order to obtain an approximation of what occurs inside the channels of the impeller and diffuser pump in terms of flow. Three different geometry conditions were initially tested to determine which is most suitable to solving the problem. After choosing the most appropriate geometry, three mesh conditions were analyzed and the obtained values were compared to the experimental characteristic curve of Head provided by the manufacturer. The results have approached the experimental curve, the simulation time and the model convergence were satisfactory if it is considered that the studied problem involves numerical analysis. After the tests with water, oil was used in the simulations. The results were compared to a methodology used in the petroleum industry to correct viscosity. In general, for models with water and oil, the results with single-phase fluids were coherent with the experimental curves and, through three-dimensional computer models, they are a preliminary evaluation for the analysis of the two-phase flow inside the channels of centrifugal pump used in ESP systems

Controle aplicado a poços com método de elevação e bombeio centrífugo submerso

The Electrical Submersible Pumping is an artificial lift method for oil wells employed in onshore and offshore areas. The economic revenue of the petroleum production in a well depends on the oil flow and the availability of lifting equipment. The fewer the failures, the lower the revenue shortfall and costs to repair it. The frequency with which failures occur depends on the operating conditions to which the pumps are submitted. In high-productivity offshore wells monitoring is done by operators with engineering support 24h/day, which is not economically viable for the land areas. In this context, the automation of onshore wells has clear economic advantages. This work proposes a system capable of automatically control the operation of electrical submersible pumps, installed in oil wells, by an adjustment at the electric motor rotation based on signals provided by sensors installed on the surface and subsurface, keeping the pump operating within the recommended range, closest to the well s potential. Techniques are developed to estimate unmeasured variables, enabling the automation of wells that do not have all the required sensors. The automatic adjustment, according to an algorithm that runs on a programmable logic controller maintains the flow and submergence within acceptable parameters avoiding undesirable operating conditions, as the gas interference and high engine temperature, without need to resort to stopping the engine, which would reduce the its useful life. The control strategy described, based on modeling of physical phenomena and operational experience reported in literature, is materialized in terms of a fuzzy controller based on rules, and all generated information can be accompanied by a supervisory system

Caracterização e quantificação de marcadores químicos do extrato hidroetanólico das folhas de Kalanchoe brasiliensis Cambess

Kalanchoe brasiliensis Cambess (Crassulaceae), commonly known as saião , coirama branca , folha grossa , is originally from Brazil and commonly found in São Paulo to Bahia, mainly in the coastal zone. Regarding of biological activities, most preclinical studies were found in the literature, mainly about the anti-inflammatory activity of extracts obtained from leaves and / or aerial parts of K. brasiliensis. As regards the chemical constitution, it has been reported mainly the presence of flavonoids in the leaves of the species, but until this moment did not knows which are the active compounds. Although it is a species widely used in traditional medicine in Brazil, there is no monograph about the quality parameters of the plant drug. In this context, this study aims to characterize and quantify the chemical markers of hydroethanolic extract (HE) from the leaves of K. brasiliensis, which can be used in quality control of plant drug and derivatives obtained from this species. The methodology was divided into two parts: i. Phytochemical study: to fractionate, isolate and characterizate of the chemical (s) marker (s) of the HE from the leaves of K. brasiliensis; ii. To Developed validate of analytical method by High Performance Liquid Chromatography (HPLC)-diode array detector (DAD) to quantify the chemical (s) marker (s) of the EH. i. The EH 50% was prepared by turbo extraction method. It was then submitted to liquid-liquid partition, obtaining dichloromethane, n-butanol and ethyl acetate (AcOEt) fractions. The AcOEt fraction was selected to continue the fractionation process, because it has a chemical profile rich in flavonoids. The acOEt fraction was submitted to column chromatography using different systems for obtaining the compound Kb1. To identify this compound, it was submitted to UV analysis ii. For quantitative analysis, the EH was analyzed by HPLC, using different methods. After selecting the most appropriate method, which showed satisfactory resolution and symmetrical peaks, it was validated according to parameters in the RE 899/2003. As result, it was obtained from the AcOEt fraction the compound Kb1 (2.7 mg). Until this moment, the basic nucleus was characterized by UV analysis using shift reagents. The partial chemical structure of the compound Kb1 was identified as a flavonol, containing hydroxyls in 3 , 4 position (ring A), 5 and 7 free (ring B) and a replacement of the C3 hydroxyl by a sugar. As the analysis were performed in the HPLC coupled to a DAD, we observed that the UV spectrum of the major peaks of EH from K. brasiliensis shown similar UV spectrum. According to the literature, it has been reported the presence of patuletin glycosydes derivatives in the leaves of this species. Therefore, it is suggested that the compound Kb1 is glycosylated patuletin derivative. Probably the sugar (s) unit(s) are linked in the C3 in the C ring. . Regarding the development of HPLC analytical method, the system used consists of phase A: water: formic acid (99,7:0,3, v / v) and phase B: methanol: formic acid (99,7:0,3, v / v), elution gradient of 40% B - 58% B in 50 minutes, ccolumn (Hichrom ®) C18 (250x4, 0 mm, 5 μm), flow rate 0.8 mL / min, UV detection at 370 nm, temperature 25 ° C. In the analysis performed with the co-injection of thecompound Kb1 + HE of K. brasiliensis was observed that it is one of the major compounds with a retention time of 12.47 minutes and had a content of 15.3% in EH of leaves from K. brasiliensis. The method proved to be linear, precise, accurate and reproducible. According to these results, it was observed that compound Kb1 can be used as a chemical marker of EH from leaves of K. brasiliensis, to assist in quality control of drug plant and its derivatives

Desenvolvimento e validação de método analítico para determinação de WE010, WE014 e WE017

The synthetic guanylhydrazones WE010 (3,5-di-tert-butil-4-hidroxibenzaldehyde-guanylhydrazone), WE014 (4-bifenilcarboxialdehydeguanylhydrazone) and WE017 (3,4-diclorobenzaldehydeguanylhydrazone) showed high cytotoxic activity in terms of percentage inhibition of cancer cells growth. However, further progress in the development of these drug candidates requires precise and convenient methods for their qualitative and quantitative analyses. The aim of this study was to develop and validate High Performance Liquid Chromatography with diode-array detection (HPLC-DAD) and Ultra Fast Liquid Chromatography with diode-array detection (UFLC-DAD) methods suitable for as simultaneous as isolated determination of studied guanylhydrazones, based on the optimization of chromatographic parameters and obtaining reduced detection times. The chromatographic analyses of analytes by HPLC were performed on C18 ACE analytical column (150 mm x 4.6 mm), with a particle size of 5.0 μm. Among all the conditions assayed, the best results of separation were obtained with a mixture of methanol:water (60:40, v/v) as the mobile phase at a flow rate 1.5mL/min and pH of 3.5 adjusted at acetic acid. The UFLC method was developed by experimetal desing techniques in order to find optimal chromatographic analytical conditions, which were achieved on XR-ODS analytical column (50 mm x 3.0 mm), with a particle size of 2,2 μm, maintained at 25 ºC. The mobile phase was consisted of methanol:water (65:35, v/v) with 0.1% triethylamine (TEA) and pH of 3.5 adjusted at acetic acid, at a flow rate 0.5 mL/min. The procedure were validated following evaluating parameters such as specificity, linearity, limits of detection (LD) and quantification (LQ), precision, accuracy and robustness, giving results within the acceptable range. Although the UFLC method shows better sensitivity (lower values of LD and LQ), robustness (lower rates of relative standard deviation) and minimize spending time and solvent, both developed methods were adequately applied to the analysis of guanylhydrazones molecules, may be used in routine of quality control laboratories. Keywords: guanylhydrazones, HPLC/DAD, UFLC/DAD, validation of analitical method

Respostas funcionais de diferentes tamanhos de Tilápia do Nilo; Oreochromis niloticus; predando zooplâncton

The Nile tilapia, Oreochromis niloticus, is an important omnivorous fish in the reservoirs of the semi-arid region of Brazil. Throughout its growth tilapia s feeding behavior changes from a visual predator of zooplankton to a filter-feeder, collecting suspended particulate matter, including planktonic organisms, through pumping. This feature results in different impacts of tilapia on plankton community as the fish grows. Aiming to quantify the functional response of different sizes of Nile tilapia on zooplankton experiments in microcosms scale in the laboratory and in mesocosm scale in the field were carried out. The data were fitted to four different models of functional response. The best fits were obtained for nonlinear models in laboratory experiments. While the experiments in mesocosms were the best settings for responses of type I (juvenile and adult tilapia) and type III (fry). The Manly's alpha index was used to evaluate the feeding selectivity of tilapia on the three main groups of the zooplankton in the experiments in mesocosms. The results show that: (i) rotifers were the preferred prey of fingerlings,(ii) copepods were rejected by fry and juvenile tilapia and (iii) adult fish fed non-selectively on copepods, cladocerans and rotifers. The functional response models obtained in this research can be applied to population models and help in modeling the dynamics of interactions between Nile tilapia and the planktonic communities in the reservoirs of the semi-arid

Avaliação de tanques de escorva utilizados em substituição à válvula-de-pé em instalações de bombeamento

A maioria das instalações de abastecimento de água utiliza bombas hidráulicas do tipo turbobombas, requerendo que o interior de sua carcaça e da tubulação de sucção esteja preenchido com água (escorvados) para que a sucção da água possa ser efetivada. O escorvamento das bombas pode ser efetuado instalando-as abaixo do reservatório de captação (bomba afogada). Quando a bomba está acima do reservatório e o escorvamento é manual, é necessário usar válvulas-de-pé, que são suscetíveis ao mau funcionamento, limitando a confiabilidade do sistema, principalmente em caso de automação. Como alternativa à válvula-de-pé, neste trabalho, foram estudados dois tanques escorva, testados no Laboratório de Hidráulica e Irrigação da FCAV/UNESP - Jaboticabal, avaliando-se situações de altura manométrica de sucção de bomba centrífuga e relações entre volume útil do tanque e volume do tubo de sucção, tendo-se concluído: a) o volume do tanque de escorva é função do volume do tubo de sucção da instalação de bombeamento e da altura manométrica de sucção; b) o volume do tanque de escorva pode ser calculado seguindo-se a Lei de Boyle, com percentagem de acréscimo que, neste estudo, foi de 10% para um modelo de tanque e de 30% para o segundo modelo.