GC analysis of organotin compounds using pulsed flame photometric detection and conventional flame photometric detection

Organotin compounds, largely used as biocides in antifouling paints, are among the most toxic materials introduced into the aquatic environment. Sensitive analytical methods are thus required to characterize their occurrence in environmental and biological matrices. The comparison between two different photometric detectors in terms of analytical performance was carried out for the analysis of organotin compounds. A flame photometric detector (FPD) and a pulsed flame photometric detector (PFPD) were optimized. Their respective sensitivity, linearity range and selectivity were evaluated. Limits of detection obtained for a tributyltin compound (TBT) were 5.0 and 0.9 pg (as Sn) for the FPD and PFPD, respectively, using a 390 nm filter. The PFPD showed higher selectivity, besides reduced gas consumption in the flame, and is very attractive for organotin compound speciation in complex environmental matrices.

Analysis of camphorquinone in composite resins as a function of shade

Objective. To identify and quantify the camphorquinone (CQ) used in different brands of composite resins as a function of the shade analyzed.Materials and methods. Filtek Z250 A3 (FZA3), Filtek Z-250 Incisal (FZI), Pyramid Enamel A1 (PEA1), Pyramid Enamel Translucent (PET), Filtek Supreme A3E (FSA3) and Filtek Supreme GT (FSGT) were used. Five hundred milligrams of each resin were weighed and then dissolved in 1.0 ml of methanol. The samples were centrifuged to accelerate the sedimentation of the inorganic particles. 0.8 ml of the supernatant solution was collected with a pipette and assessed under gas chromatography coupled to the mass spectrometer (GC-MS). The results were compared to pure CQ solutions, used as a standard. Student's t-test, (p = 0.05) significant at the level of 5%, compared the results of each brand shade.Results. A smaller amount of camphorquinone was found in Filtek Z-250 (FZI) resin incisal shade when compared to (FZA3) A3 shade. on the other hand, Filtek Supreme resin featured a statistically larger camphorquinone amount in the incisal shade. in Pyramid Enamel resin camphorquinone was found only in shade Al, while the photoinitiator used in the Translucent shade was not identified.Significance. Based on the data obtained, it is possible to conclude that a single composite resin brand may feature differences in amount and type of photoinitiator used. (C) 2006 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Kinetic parameters of polymer degradation by SAPO-37

High density poly(ethylene) has been submitted to thermal degradation alone, and in the presence of silicoaluminophosphate SAPO-37. The processes were carried out in a reactor connected on line to a gas chromatograph/mass spectrometer in order to analyze the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature until 800 degreesC, under nitrogen dynamic atmosphere, with multiple heating rates. From TG curves, the activation energy related to degradation process was calculated using the Flynn and Wall multiple heating rate kinetic model for pure polymer (PE) and for polymer in the presence of catalyst (PE/S37). SAPO-37 showed good selectivity for low molecular mass hydrocarbons in PE catalytic degradation.

Thermodynamic and economic analyses of a Brazilian natural gas thermal power plant

In this work, thermodynamic and economic analyses are applied to a Brazilian thermal power plant operating with natural gas. The analyses are performed in two cases: the current configuration and the future configuration. The current configuration is constituted by four gas turbines which operate in open cycle. The future configuration is obtained by a plant repowering by addition of four recovery boilers, two steam turbines and others equipment and accessories necessary to operate in combined cycle. In order to obtain the performance parameters, energetic and exergetic analyses for each case considered are carried out. on the other hand, thermoeconomic analysis provides means to evaluate the influences of the capital and fuel costs in the composition of the electricity costs. Techniques of investment analysis are also applied to the new configuration and from the results obtained it is possible to verify the advantages of the modifications.

Screening Brazilian C gasoline quality: Application of the SIMCA chemometric method to gas chromatographic data

A total of 2400 samples of commercial Brazilian C gasoline were collected over a 6-month period from different gas stations in the São Paulo state, Brazil, and analysed with respect to 12 physicochemical parameters according to regulation 309 of the Brazilian Government Petroleum, Natural Gas and Biofuels Agency (ANP). The percentages (v/v) of hydrocarbons (olefins, aromatics and saturated) were also determined. Hierarchical cluster analysis (HCA) was employed to select 150 representative samples that exhibited least similarity on the basis of their physicochemical parameters and hydrocarbon compositions. The chromatographic profiles of the selected samples were measured by gas chromatography with flame ionisation detection and analysed using soft independent modelling of class analogy (SIMCA) method in order to create a classification scheme to identify conform gasolines according to ANP 309 regulation. Following the optimisation of the SIMCA algorithm, it was possible to classify correctly 96% of the commercial gasoline samples present in the training set of 100. In order to check the quality of the model, an external group of 50 gasoline samples (the prediction set) were analysed and the developed SIMCA model classified 94% of these correctly. The developed chemometric method is recommended for screening commercial gasoline quality and detection of potential adulteration. (c) 2007 Elsevier B.V. All rights reserved.

Influence of experimental factors on results of thermogravimetric analysis

Thermogravimetric results are influenced by a series of experimental factors, such as furnace heating rate and atmosphere, velocity of carrier gas, sample mass, etc. In this work a practical evaluation of these parameters are showed for calcium oxalate, with teaching objectives, considering that undergraduate text books discuss but do not show experimental details for these cases.

Determination of the sodium monofluoroacetate in serum by gas chromatography

Sodium monofluoroacetate (NAFAc) has been widely used for vertebrate pest control, such as rabbits in Australia. However NAFAc is extremely toxic to all vertebrates and its use is restricted. Although this compound is stringently restricted, the occurrence of accidental and homicidal poisoning is no ever-present possibility.The method developed in this work shows the applicability of SPE with alumina cartridges for the extraction of NAFAc from serum samples. The method is efficient with recoveries of at least 96.8% from spiked serum. The samples were subsequently derivatized with dicyclohexylcabodiimide (DCC), using 2,4-dichloroaniline (DCA), to make the product volatile for GC analysis.

Analysis of cement slurries by inductively coupled plasma optical emission spectrometry with axial viewing

The feasibility of Portland cement analysis by introduction of slurries in an inductively coupled plasma optical emission spectrometer (ICP-OES) with axial viewing has been evaluated. After a fast manual grinding of the cement samples, owing to the pulverized state of this material, 0.1% m/v slurries were prepared in 1% v/v HCl. The calibration was performed adopting two strategies: one based on slurries prepared from different masses (50, 75, 100 and 125 mg) of a Portland cement standard reference material (NIST SRM 1881), and the other one based on aqueous reference solutions. A complete analysis of cement for major (Al, Ca, Fe, Mg and Si), minor and trace elements (Mn, P, S, Sr and Ti) was accomplished. Both strategies led to accurate results for commercial Portland cement samples, except for Si and Ti. for which the calibration with aqueous reference solutions resulted in low values. Applying a paired t-test it was shown that most results were in agreement at a 95% confidence level with a conventional fusion decomposition procedure. The ICP-OES with axial viewing and end-on gas configuration for removal of the recombination plasma zone was effective for cement slurry analysis without any undesirable particle deposition in the pre-optics interface and without severe spectral interferences. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Determination of organochlorine pesticides and polychlorinated biphenyls residues in municipal solid waste compost by gas chromatography with electron-capture detection

A simple and efficient method for the simultaneous gas chromatographic determination of ten organochlorine pesticides (alpha-HCH, beta-HCH, gamma-HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, endrin, and dieldrin) and six congeners of PCBs (PCB 28, 52, 118, 138, 153, and 180) in municipal solid waste compost is described. The procedure involves a solid-phase dispersion matrix using celite as dispersant sorbent, alumina as clean up sorbent and hexane-dichloromethane (7:3, v/v) mixture as eluting solvent. An additional purification step with copper was necessary to eliminate sulphur. Analysis of the sample was performed by GC-ECD. The method was validated with fortified samples at two concentration levels (0.025 and 0.05 mg kg(-1)). Average recovery ranged from 77 to 121% with relative standard deviation between 1 and 18%. The detection limits, which ranged from 0.003 to 0.01 mg kg-1, were lower than those established by the Baden-Wurttemberg directive (0.033 mg kg(-1)).

ASSESSMENT of POLYATOMIC INTERFERENCES ELIMINATION USING A COLLISION REACTION INTERFACE (CRI) FOR INORGANIC ANALYSIS of FUEL ETHANOL BY ICP-QMS

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

Direct analysis of biodiesel microemulsions using an inductively coupled plasma mass spectrometry

An analytical procedure for direct introduction of biodiesel samples into an inductively coupled plasma mass spectrometer (ICP-MS) by using microemulsion for sample preparation was developed here. Cadmium, Co, Cu, Mn, Ni, Pb, Ti, and Zn were determined in biodiesel microemulsified samples prepared from different oleaginous sources (African palm, castor beans, palm, soybeans and an unknown oleaginous). Microemulsions were prepared using 0.25 mL Triton X-100, 0.25 mL 20% v v(-1) HNO(3), 0.50 mL biodiesel sample and 4.0 mL n-propanol. Argon-oxygen mixture was added to the plasma as auxiliary gas for correcting matrix effects caused by the high carbon load due to biodiesel microemulsions. The oxygen gas flow rate was set in 37.5 mL min(-1). The accuracy of the developed procedure was evaluated by applying addition-recovery experiments for biodiesel samples from different sources. Recoveries varied from 76.5 to 116.2% for all analytes but Zn in castor beans biodiesel sample (65.0 to 76.2%). Recoveries lower than 86.6% were obtained for palm biodiesel sample, probably due to matrix effects. Detection limits calculated by using oxygen in the composition of the auxiliary gas added to the plasma were higher than those calculated without using it, probably due to the highest formation of oxides. Despite oxides formation, best analytical performance was reached by using oxygen as auxiliary gas and by proper correction of transport interferences. The developed procedure based on microemulsion formation was suitable for direct introduction of biodiesel samples in ICP-MS. (C) 2010 Elsevier B.V. All rights reserved.

Sol-gel synthesis of mesoporous CaCu3Ti4O12 thin films and their gas sensing response

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Gauge-independent analysis of 2D-gravity

In this note we show that the induced 2D-gravity SL(2, ℝ) currents can be defined in a gauge-independent way although they manifest themselves as generators of residual symmetries only in some special gauges. In the Coulomb gas representation we investigate two approaches, namely one resembling string field theory and another that emphasizes the SL(2, ℝ) structure in the phase space. In the conformal gauge we propose a solution of the Liouville theory in terms of the SL(2, ℝ) currents.

Gas Chromatographic Determination of Cyprodinil, Fludioxonil, Pyrimethanil, and Tebuconazole in Grapes, Must, and Wine

A rapid and simple gas chromatographic method for determinating cyprodinil, fludioxonil, pyrimethanil, and tebuconazole in grapes, must, and wine is described. An on-line microextraction method was used with a one-step extraction-partition procedure. Nitrogen-phosphorus and mass spectrometric detectors were used, because of their low sensitivity and high selectivity. Because of high selectivity of detector, no cleanup was necessary and the extract was concentrated 5 times. Recoveries from fortified grapes, must, and wine ranged from 93 to 110%. Limits of determination were 0.05 mg/kg for cyprodinil and pyrimethanil and 0.10 mg/kg for fludioxonil and tebuconazole.

Gas-chromatographic determination of deltamethrin in crops

A rapid and economical method is described for the determination of deltamethrin in wheat, rice, peanuts and corn. It is based on simultaneous extraction and clean-up on a column packed with alumina and silica gel using n-hexane-ethyl ether (8:2, v/v), followed by a derivatization step and gas-chromatographic analysis. Recoveries from fortified cereal and peanut samples were determined at four concentration levels and ranged from 73 to 109%. The detection limits were 0.01 to 0.03 mg/ kg. This method simplifies the traditional procedures in terms of sample size, solvent consumption and analysis time. © Springer-Verlag 1998.