Amostragem de compostos orgânicos voláteis no ar utilizando a técnica de microextração em fase sólida

The sampling of volatile organic compounds using solid phase microextraction is reviewed and its principles are described. The development and application of solid phase microextraction in the sampling of VOCs are presented and discussed.

Estimativa do fluxo de amônia na interface ar-mar na Baía de Guanabara: estudo preliminar

In the begining of April 2004, concentrations of NHx (NH3 + NH4+) were measured in surface waters of the Guanabara Bay. Concentrations varied from 2 to 143 mmol L-1. Ammonia exchange at the air-sea interface was quantified using a numerical model. No measurement of NH3 concentration in air (c air) was performed. Thus, calculations of NH3 flux were based on the assumptions of c air = 1 and 5 µg m-3. Fluxes were predominantly from the water to the atmosphere and varied from -20 to almost 3500 µg N m-2 h-1.

Espectrometria de massas com ionização por "electrospray": processos químicos envolvidos na formação de íons de substâncias orgânicas de baixo peso molecular

An overview of the current literature on the chemical processes involved in the ion formation from low molecular weight organic compounds by electrospray ionization mass spectrometry is given.

Análise quiral por espectrometria de massas através da utilização do método cinético

Novel and quantitative mass spectrometry methods for rapid and accurate enantiomeric excess determination are presented. These methodologies use electrospray ionization (ESI) and mass spectrometry (MS) to detect and analyze, via collision-induced dissociation (CID), mass-selected transition metal complexes that promote enantio especific interactions. The data from CID are conveniently treated by the kinetic method, a sensitive linear free energy method of treating mass spectrometric results. Four different variations of this methodology are described: single ratio method (S R), quotient ratio method (Q R), fixed ligand method (S Rfixed), and quotient ratio method with fixed ligand (Q Rfixed). These individual methods are compared and their main features discussed in detail.

Determinação de resíduos de cloranfenicol em amostras de leite e mel industrializados utilizando a técnica de espectrometria de massas em "tandem" (CLAE-EM/EM)

The present work shows a method for the determination of chloramphenicol (CAP) antibiotic in milk, powder milk and honey. The solid phase extraction and liquid-liquid extraction were applied as a clean-up and pre-concentration strategies followed by LC-ESI/MS/MS analysis. The recovery was studied for different fortification levels from 0.05 to 1.00 µg L-1 in milk, showing values between 91 101% and RSD bellow 8.0%, while honey was spiked with a concentration of 0.20 µg kg-1 yelding a mean recovery of 83% and RSD of 6.5%. The quantification transition 321>152 showed a LOD of 0.52 ng kg-1 and LOQ of 1.85 ng kg-1.

Influência da temperatura do ar de secagem sobre o teor e a composição química do óleo essencial de Lippia alba (Mill) N. E. Brown

Leaves of Lippia alba were submitted to six different drying treatments, using air at ambient temperature and heated up to 80 °C. The essential oil was extracted by steam distillation and analyzed by GC-MS. For the dried leaves, the oil content was reduced by 12 to 17% when compared with the fresh plant (0.66%). The major oil component was citral, representing 76% for the fresh plant, and varying from 82 to 84% for the dried material. These results showed that L. alba can be submitted to a drying process of up to 80 ºC without degradation and/or loss of the major, [LC1] active component.

Desenvolvimento e validação de metodologia de análise de misturas biodiesel: diesel utilizando cromatografia gasosa-espectrometria de massas

The aim of this work was to develop and validate a method of analysis of biodiesel:diesel blends using HRGC-MS in SIM mode. The proposed method is applicable to biodiesel from linoleic oils, such as soybean oil. The following results were obtained: linearity over the methyl linoleate concentration range of 250-2500 mg L-1 (R² > 0.999); limits of detection and quantification of 2 and 5 mg L-1, respectively; recovery from 82 to 96% of biodiesel in diesel and repeatability < 2% (RSD). Comparison between two operators showed that it is not necessary the same operator to do the analysis.

Principais carbonilas no ar de locais públicos no Rio de Janeiro

An air quality evaluation of indoor environments with focus on lower carbonyls was carried out in 50 public places using TO-11A methodology. Formaldehyde levels (ranging from 12.5 to 1034 mg m-3) were above the threshold limit in 49 of 50 analyzed samples while acetaldehyde (ranging from 5.2 to 840 mg m-3) and acetone (ranging from 5.5 to 4839 mg m-3) were respectively bellow the limits of OSHA and NIOSH in all samples. However all samples were bellow the threshold limits suggested by the Brazilian legislation - NR-15. A correlation study between the carbonyls and temperature and humidity was also done.

O estado da arte da cromatografia associada à espectrometria de massas acoplada à espectrometria de massas na análise de compostos tóxicos em alimentos

Chromatography combined with several different detection systems is one of the more used and better performing analytical tools. Chromatography with tandem mass spectrometric detection gives highly selective and sensitive analyses and permits obtaining structural information about the analites and about their molar masses. Due to these characteristics, this analytical technique is very efficient when used to detect substances at trace levels in complex matrices. In this paper we review instrumental and technical aspects of chromatography-tandem mass spectrometry and the state of the art of the technique as it is applied to analysis of toxic substances in food.

Seqüenciamento de peptídeos usando espectrometria de massas: um guia prático

This paper introduces the basics of peptide mass spectra interpretation applied to proteomics and is directed to chemists, biochemists and biologists. The manuscript presents a well detailed protocol aiming to serve as a first choice guide for understanding peptide sequencing. The tutorial was elaborated based on both a thorough bibliographic revision and the author's experience. In order to prove the applicability of the proposed guide, spectra obtained on different instruments have been successfully interpreted by applying the presented rational.

Aplicação da química quântica computacional no estudo de processos químicos envolvidos em espectrometria de massas

The field of application of mass spectrometry (MS) has increased considerably due to the development of ionization techniques. Other factors that have stimulated the use of MS are the tandem mass spectrometry (MS/MS) and sequential mass spectrometry (MSn) techniques. However, the interpretation of the MS/MS and MSn data may lead to speculative conclusions. Thus, various quantum chemical methods have been applied for obtaining high quality thermochemical data in gas phase. In this review, we show some applications of computational quantum chemistry to understand the formation and fragmentation of gaseous ions of organic compounds in a MS analysis.

Otimização da análise isotópica de UF6 utilizando-se a técnica de espectrometria de massas por quadrupolo

A procedure for determining of the isotope ratio 235U/238U in UF6 samples was established using a quadrupole mass spectrometer with ionization by electron impact. The following items were optimized in the spectrometer: the parameters in the ion source that provided the most intense peak, with good shape, for the most abundant isotope; the resolution that reduced the non linear effects and the number of analytical cycles that reduced the uncertainty in the results. The measurement process was characterized with respect to the effects of mass discrimination, linearity and memory effect.

Fluxos de óxido nitroso na interface ar-mar na Baía de Guanabara

In Surface water concentrations of N2O were measured at 37 stations in Guanabara Bay and fluxes estimated across the air-sea interface. Concentrations averaged 8.2 ± 2.2 nmol L-1 and 90% of the stations showed supersaturation averaging 33%. N2O fluxes were estimated using a two-film model which is given by the product of the concentration difference across the film and the gas transfer coefficient (k w). Two parametrizations of k w were used which provided average fluxes of 0.3 and 3.0 µg N m-2 h-1. Flux measurements using floating chambers (not reported here) seem to agree with the upper limit of these estimates.

Parâmetros bioquímicos foliares das espécies Licania tomentosa (Benth.) e Bauhinia forficata (Link.) para avaliação da qualidade do ar

Foliar analysis of biochemical parameters were carried out in order to investigate the influence of air pollutants on two tropical tree species (Licania tomentosa (Benth.) and Bauhinia forfícata (Link.)). Special attention was given to tropospheric ozone due to the fact that concentration levels in the region were found to be up to 140 µg m-3 for a 4 h average time, which is well above the value that can cause injuries to orchides and tobacco (59 µg m-3). Other pollutants such as nitrogen and sulphur oxides were measured and their ambient concentrations were also associated to biochemical alterations in the investigated species.

Determinação da relação siringila/guaiacila da lignina em madeiras de eucalipto por pirólise acoplada à cromatografia gasosa e espectrometria de massas (PI CG/EM)

The use of analytical pyrolysis combined with gas chromatography/mass spectrometry (Py-GC/MS) to determine the syringyl/guaiacyl ratio (S/G) in lignins from Eucalyptus spp woods was investigated. Sample of E. grandis and "E. urograndis" wood, with and without extractives, were subjected to pyrolysis from 300 ºC to 600 ºC. The products that results from pyrolysis were identified by mass spectrometry and the S/G ratio was determined based on the areas of the peaks corresponding to the guaiacyl and syringyl derivatives. The best S/G estimation is achieved when pyrolysis is carried out at 550 ºC. Extractives and carbohydrate present in the woods do not interfere with the results.