Evaluation of pesticide adsorption in gas chromatographic injector and column

Components in complex matrices can cause variations in chromatographic response during analysis of pesticides by gas chromatography. These variations are related to the competition between analytes and matrix components for adsorption sites in the chromatographic system. The capacity of the pesticides chlorpyrifos and deltamethrin to be adsorbed in the injector and chromatographic column was evaluated by constructing three isotherms and changing the column heating rate to 10 and 30 ºC min-1. By using ANCOVA to compare the slope of calibration graphs, results showed that the higher the injector temperature (310 ºC) the lower the pesticide adsorption. Also, deltamethrin influenced the adsorption of chlorpyrifos on the column chromatographic.

Specificity and selectivity improvement in doping analysis using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry

Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry was used for the identification of forty doping agents. The improvement in the specificity was remarkable, allowing the resolution of analytes that could not be done by one-dimensional chromatographic systems. The sensitivity observed for different classes of prohibited substances was clearly below the value required by the World Anti-Doping Agency. In addition time-of-flight mass spectrometry gives full spectrum for all analytes without any interference from the matrix, resulting in selectivity improvements. These results could support the implementation of an exhaustive monitoring approach for hundreds of doping agents in a single injection.

KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68%) and selectivity (100%) for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Evaluation of gas diffusion electrodes as detectors in amperometric hydrogen sensors

This work is directed to the study and evaluation of gas diffusion electrodes as detectors in hydrogen sensors. Electrochemical experiments were carried out with rotating disk electrodes with a thin porous coating of the catalyst as a previous step to select useful parameters for the sensor. An experimental arrangement made in the laboratory that simulates the sensor was found appropriate to detect volumetric hydrogen percentages above 0.25% in mixtures H2:N2. The system shows a linear response for volumetric percentages of hydrogen between 0.25 and 2 %.

Initial development and gas exchange of Talisia subalbens (Mart.) Radlk. under different shading conditions

Ecophysiological studies under semi-controlled conditions in nurseries and greenhouses are essential to enable the use of native species to recover degraded areas and for commercial planting. Talisia subalbens (Mart) Radlk, 'cascudo', is a native fruiting species of the Cerrado on the verge of extinction. The ecophysiological performance of this species was evaluated in nursery conditions under different levels of shading (full sunshine, 30%, 50% and 70%). Initial growth, biomass allocation, gas exchange and chlorophyll content of the plants were analyzed. Full sunshine cultivated plants showed a higher accumulation of total, shoot, and root dry biomass. There was no significant difference in the root/shoot ratio among the treatments. Seedlings cultivated under full sunshine and 30% shading showed higher values for height, basal diameter, and leaf area. Differences in stomata conductance and photosynthesis rate were not observed among the different shading levels. Plants cultivated under 70% of shading had higher contents of chlorophyll a, b, and total. During the initial phase with higher levels of radiation were fundamental for the development of T. subalbens seedlings.

GAS EXCHANGE IN YOUNG PLANTS OF Tabebuia aurea(Bignoniaceae Juss.) SUBJECTED TO FLOODING STRESS1

ABSTRACT The Paratudo (Tabebuia aurea) is a species occurring in the Pantanal of Miranda, Mato Grosso do Sul, Brazil, an area characterized by seasonal flooding. To evaluate the tolerance of this plant to flooding, plants aged four months were grown in flooded soil and in non-flooded soil (control group). Stomatal conductance, transpiration and CO2 assimilation were measured during the stress (48 days) and recovery (11 days) period, totalling 59 days. The values of stomatal conductance of the control group and stressed plants at the beginning of the flooded were 0.33 mol m-2s-1 and reached 0.02 mol m-2 s-1 (46th day) at the end of this event. For the transpiration parameter, the initial rate was 3.1 mol m s-1, and the final rate reached 0.2 or 0.3 mol m-2 s-1 (47/48 th day). The initial photosynthesis rate was 8.9 mmol m-2s-1 and oscillated after the sixth day, and the rate reached zero on the 48th day. When the photosynthesis rate reached zero, the potted plants were dried, and the rate was analyzed (11th day). The following values were obtained for dried plants: stomatal conductance = 0.26 mol m-2 s-1, transpiration rate = 2.5 mol m-2 s-1 and photosynthesis rate = 7.8 mmol m-2 s-1. Flooded soil reduced photosynthesis and stomatal conductance, leading to the hypertrophy of the lenticels. These parameters recovered and after this period, and plants exhibited tolerance to flooding stress by reducing their physiological activities.

Microgeneration of electricity with producer gas in dual fuel mode operation

Among the alternatives to meet the increasing of world demand for energy, the use of biomass as energy source is one of the most promising as it contributes to reducing emissions of carbon dioxide in the atmosphere. Gasification is a technological process of biomass energy production of a gaseous biofuel. The fuel gas has a low calorific value that can be used in Diesel engine in dual mode for power generation in isolated communities. This study aimed to evaluate the reduction in the consumption of oil Diesel an engine generator, using gas from gasification of wood. The engine generator brand used was a BRANCO, with direct injection power of 7.36 kW (10 HP) coupled to an electric generator 5.5 kW. Diesel oil mixed with intake air was injected, as the oil was injected via an injector of the engine (dual mode). The fuel gas was produced in a downdraft gasifier. The engine generator was put on load system from 0.5 kW to 3.5 kW through a set of electrical resistances. Diesel oil consumption was measured with a precision scale. It was concluded that the engine converted to dual mode when using the gas for the gasification of wood decreased Diesel consumption by up to 57%.

Evaluation of the heating of broilers in shed by means of gas hoods and underfloor heating

This study was conducted to evaluate and compare the behavior of the heating inside poultry shed through gas hood and underfloor heating. The experiment was conducted in poultry shed belonging to the Federal Institute of Education, Science and Technology of Triângulo Mineiro Region, Uberlândia city – state of Minas Gerais (MG), Brazil. The dimensions of the shed are 24 meters long and 9.6 meters wide and with a ceiling height of 3.2 meters. The temperature was measured with an optical thermometer of Minipa brand, MT 350 model. It was used, to the analysis of temperature behavior, the public domain software FEMM 4.2, which uses finite elements techniques, with data collected from two lots. Underfloor heating is made using hot water flowing through a serpentine type system, which is installed below the bed; this hot water is from solar heaters. An energetic and economic assessment of the warming shed for raising chickens was realized. From the results obtained with the simulations, it may observe that the heating through the floor provides a more homogeneous distribution of temperature when compared with the hood heating. The flow of heat is upwards supplying, thus, the greatest need of heating of the bird, which is the pectoral part.

Blood-gas and electrolyte values for Amazon parrots (Amazona aestiva)

The aim was to provide reference data for blood gas/acid-base status and electrolytes for non-anesthetized Amazon parrots (Amazona aestiva). Thirty-five adult parrots from Tietê ecologic park were utilized. Arterial blood (0.3ml) samples were anaerobically collected from the superficial ulnar artery in heparinized (sodium heparin) 1-ml plastic syringes. The samples were immediately analyzed through a portable analyzer (i-STAT*, Abbot, Illinois, USA) with cartridges (EG7+). These data were grouped in such a way as to present both mean and standard deviation: body weight (360±37g), respiratory rate (82±33 b/m), temperature (41.8±0.6°C), hydrogen potential (7.452±0.048), carbon dioxide partial pressure (22.1±4.0mmHg), oxygen partial pressure (98.1±7.6mmHg), base excess (-7.9±3.1), plasma concentration of bicarbonate ions (14.8±2.8mmol/L), oxygen saturation (96.2±1.1%), plasma concentration of sodium (147.4±2.2mmol/L), plasma concentration of potassium (3.5±0.53mmol/L), plasma concentration of calcium (0.8±0.28mmol/L), hematocrit (38.7±6.2%) and concentration of hemoglobin (13.2±2.1g/dl). This study led us to conclude that, although the results obtained showed hypocapnia and low values of bicarbonate and base excess, when compared to other avian species, these data are very similar. Besides, in spite of the equipment being approved only for human beings, it was considered simple and very useful in the analysis of avian blood samples. By using this equipment we were able to provide references data for non-anaesthetized Amazon parrots.

Parameter optimization of AC rectangular wave outputs for aluminum cold wire GTAW

The objective of this work was to optimize the parameter setup for GTAW of aluminum using an AC rectangular wave output and continuous feeding. A series of welds was carried-out in an industrial joint, with variation of the negative and positive current amplitude, the negative and positive duration time, the travel speed and the feeding speed. Another series was carried out to investigate the isolate effect of the negative duration time and travel speed. Bead geometry aspects were assessed, such as reinforcement, penetration, incomplete fusion and joint wall bridging. The results showed that currents at both polarities are remarkably more significant than the respective duration times. It was also shown that there is a straight relationship between welding speed and feeding speed and this relationship must be followed for obtaining sound beads. A very short positive duration time is enough for arc stability achievement and when the negative duration time is longer than 5 ms its effect on geometry appears. The possibility of optimizing the parameter selection, despite the high inter-correlation amongst them, was demonstrate through a computer program. An approach to reduce the number of variables in this process is also presented.

A quality and cost approach for welding process selection

The aim of this work was to propose, apply and evaluate a methodical approach to select welding processes in a productive environment based on market requirements of Quality and Costs. A case study was used. The welds were carried out in laboratory, simulating the joint conditions of a manufacturer and using several welding processes: SMAW, GTAW, pulsed GTAW, GMAW with CO2 and Ar based shielding gases and pulsed GMAW. For Quality analysis geometrical aspects of the beads were considered and for Cost analysis, welding parameters and consumable prices. Quantitative indices were proposed and evaluated. After that, evaluation of both Quality and Costs was done, showing to be possible to select the most suitable welding process to a specific application, taking into account the market conditions of a company.

Gas-solid two-phase flow in the riser of circulating fluidized beds: mathematical modelling and numerical simulation

A mathematical model is developed for gas-solids flows in circulating fluidized beds. An Eulerian formulation is followed based on the two-fluids model approach where both the fluid and the particulate phases are treated as a continuum. The physical modelling is discussed, including the formulation of boundary conditions and the description of the numerical methodology. Results of numerical simulation are presented and discussed. The model is validated through comparison to experiment, and simulation is performed to investigate the effects on the flow hydrodynamics of the solids viscosity.

Hydrodynamics Characteristics and Gas-Liquid Mass Transfer in a Three Phase Fluidized Bed Reactor

This paper presents the experimental characterization of hydrodynamics and gas-liquid mass transfer in a three-phase fluidized bed containing polystyrene and nylon particles. The influence of gas and liquid velocities on phase holdups and volumetric gas-liquid mass transfer coefficient was investigated for flow conditions similar to those applied in biotechnological process. The phase holdups were obtained by the pressure profile technique. The volumetric gas-liquid mass transfer coefficient was obtained adjusting the experimental concentration profiles of dissolved oxygen in the liquid phase with the predictions of the axial dispersion model. According to experimental results the liquid holdup increases with the gas velocity, whereas the solid holdup decreases. The gas holdup increases significantly with the increase in gas velocity, and it shows for the three-phase fluidized bed comparable values or larger than those of bubble column. The volumetric gas-liquid mass transfer coefficient increases significantly with an increase in the air velocity for both bubble column and fluidized beds. In addition, in the operational condition of high liquid velocity, the presence of low-density particles in the bed increased the gas-liquid mass transfer, and thus the volumetric mass transfer coefficient values obtained in the fluidized bed were comparable or larger than those of bubble column.

Comparison of the quantification of caffeine in human plasma by gas chromatography and ELISA

In the present study we evaluated the precision of the ELISA method to quantify caffeine in human plasma and compared the results with those obtained by gas chromatography. A total of 58 samples were analyzed by gas chromatography using a nitrogen-phosphorus detector and routine techniques. For the ELISA test, the samples were diluted to obtain a concentration corresponding to 50% of the absorbance of the standard curve. To determine whether the proximity between the I50 of the standard curve and that of the sample would bring about a more precise result, the samples were divided into three blocks according to the criterion of difference, in modulus, of the I50 of the standard curve and of the I50 of the sample. The samples were classified into three groups. The first was composed of 20 samples with I50 up to 1.5 ng/ml, the second consisted of 21 samples with I50 ranging from 1.51 to 3 ng/ml, and the third of 17 samples with I50 ranging from 3.01 to 13 ng/ml. The determination coefficient (R² = 0.999) showed that the data obtained by gas chromatography represented a reliable basis. The results obtained by ELISA were also reliable, with an estimated Pearson correlation coefficient of 0.82 between the two methods. This coefficient for the different groups (0.88, 0.79 and 0.49 for groups 1, 2 and 3, respectively) showed greater reliability for the test with dilutions closer to I50.