Microextração em fase sólida, usando a derivatização on-line com bis(trimetilsilil)trifluoroacetamida, cromatografia a gás e espectrometria de massas, foi avaliada para a quantificação de 3-cloro-4-(diclorometil)-5-hidróxi-2(5H)-furanona (MX) em amostras de água. Foram usadas fibras de diferentes polaridades empregando a amostragem por imersão e por headspace. Para o sistema de imersão, foram avaliados vários parâmetros que afetam a extração de MX, como pH, salinidade, temperatura e tempo de extração. O método otimizado (fibra de poliacrilato; 20% Na2SO4; pH 2,0; 60 min; 20 °C) foi aplicado para águas cloradas proveniente de reservatórios de abastecimento de água-amostras naturais e amostras com adição de MX (50 ng L-1 e 100 ng L-1). A recuperação de MX variou de 44 a 72%. A quantificação do MX em amostras de água foi feita por padrão externo empregando o modo de monitoramento de íon selecionado. O coeficiente de correlação (0,98%), o desvio padrão relativo (5%), o limite de detecção (30 ng L-1) e o limite de quantificação (50 ng L-1) foram obtidos a partir da curva analítica.

Solid-phase microextraction, using on-line bis(trimethylsilyl)trifluoroacetamide derivatisation, gas chromatography, and mass spectrometry, was evaluated in the quantification of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) in water samples. Fibres encompassing a wide range of polarities were used with headspace and direct immersion sampling. For the immersion procedure, various parameters affecting MX extraction, including pH, salinity, temperature, and extraction time were evaluated. The optimised method (polyacrylate fibre; 20% Na2SO4; pH 2.0; 60 min; 20 °C) was applied for reservoir chlorinated water samples-either natural or spiked with MX (50 ng L-1 and 100 ng L-1). The recovery of MX ranged from 44 to 72%. Quantification of MX in water samples was done using external standard and the selected ion monitoring mode. Correlation coefficient (0.98%), relative standard deviation (5%), limit of detection (30 ng L-1) and limit of quantification (50 ng L-1) were obtained from calibration curve.

The environmental impact of detergents and other consumer products is behind the continued interest in the chemistry of the surfactants used. Of these, linear alkylbenzene sulfonates (LASs) are most widely employed in detergent formulations. The precursors to LASs are linear alkylbenzenes (LABs). There is also interest in the chemistry of these hydrocarbons, because they are usually present in commercial LASs (due to incomplete sulfonation), or form as one of their degradation products. Additionally, they may be employed as molecular tracers of domestic waste in the aquatic environment. The following aspects are covered in the present review: The chemistry of surfactants, in particular LAS; environmental impact of the production of LAS; environmental and toxicological effects of LAS; mechanisms of removal of LAS in the environment, and methods for monitoring LAS and LAB, the latter in domestic wastes. Classical and novel analytical methods employed for the determination of LAS and LAB are discussed in detail, and a brief comment on detergents in Brazil is given.

Compostos orgânicos voláteis, tais como hidrocarbonetos oxigenados, hidrocarbonetos alifáticos e aromáticos foram medidos no ar interno de dois túneis urbanos da cidade de São Paulo, Brasil. Nesses túneis são freqüentes os congestionamentos de tráfico com números expressivos de veículos com controle de emissão inadequada. São Paulo, uma cidade altamente poluída, apresenta uma frota atípica de veículos com uma variedade grande de misturas de combustíveis, incluindo os oxigenados. Nesse trabalho, foram feitas medidas no ar interno e externo do túnel para avaliar os níveis dos poluentes emitidos diretamente por veículos e aqueles formados fotoquimicamente na atmosfera. No túnel (A), onde circulam apenas veículos leves movidos principalmente por gasool, uma mistura contendo 78-80% (v/v) gasolina e 20-25% etanol, as razões de formaldeído/acetaldeído foram < 1; e no túnel (B), onde circulam veículos leves principalmente movidos a gasool e veículos pesados movidos a diesel, essas razões foram aproximadamente igual a 1. Em ambos os túneis, as razões ácido fórmico/ácido acético foram bem mais baixas do que 1. O benzaldeído foi sugerido como sendo um possível traçador de emissões de veículos leves movidos a gasool. Os n-alcanos foram os compostos mais abundantes (níveis semelhantes em ambos os túneis) e, em seguida os compostos carbonílicos (níveis mais altos em B) e os compostos aromáticos (níveis mais altos em A). Foram encontrados níveis semelhantes de ácidos orgânicos, espécies minoritárias, em ambos os túneis. Os resultados desse estudo mostram que poluentes tóxicos estão presentes em níveis significativos nos dois túneis. No túnel (A) foram encontrados razões de mistura de 39,2 e 24,8 ppbv para os agentes carcinogênicos formaldeído e benzeno; no túnel (B) um valor máximo de 34,5 ppbv foi encontrado para o acetaldeído, um provável agente carcinogênico. Estudos futuros devem ser feitos para estimar os níveis de exposição de poluentes tóxicos no ar para ocupantes de veículos, uma vez que essas pessoas passam um tempo significativo dentro de túneis urbanos.

Volatile organic compounds, such as oxygenated hydrocarbons, aliphatic and aromatic hydrocarbons were measured in ambient air from two distinct urban tunnels in São Paulo City, Brazil, in special, at rush hours. In these tunnels, traffic jams with significant numbers of vehicles with inadequate emission controls are frequent. São Paulo, a highly polluted city, has an unconventional mix of vehicle types in that a variety of gasoline blends, including oxygenated ones are used. Inside and outside tunnel measurements were performed to evaluate pollutant levels originated from direct vehicular emissions and formed by atmospheric photochemistry. Formaldehyde/acetaldehyde ratios of tunnel (A) circulating only light-duty vehicles fueled mainly with gasohol, a mixture containing 78-80% (v/v) gasoline and 20-25% ethanol, were < 1; ratios of tunnel (B) circulating light-duty vehicles fueled mainly with gasohol and heavy diesel vehicles, were approximately equal to 1. Formic acid/acetic acid ratios of both tunnels were much lower than 1. Benzaldehyde was suggested as a possible tracer of light-duty gasohol vehicular emissions. n-alkanes were the most abundant compound class (similar levels in both tunnels) followed by carbonyl compounds (higher levels in B), and aromatics compounds (higher levels in A). Organic acids, the minor species, were found at similar levels in both tunnels. Results of this survey show that toxic pollutants are present at significant levels in both tunnels. Formaldehyde and benzene, human carcinogenic agents, presented maximum mixing ratios of 39.2 and 24.8 ppbv, respectively, inside tunnel A; acetaldehyde, a probable human carcinogenic, reached a maximum of 34.5 ppbv inside tunnel B. Since vehicle occupants that spend a significant time in urban tunnels are commonly exposed to toxic pollutant emissions, future extensive studies should be done in order to estimate exposure levels of toxic ambient air pollutants for these people.

Níveis ambientais diurnos de ácido fórmico e acético foram medidos na atmosfera da cidade de São Paulo no inverno e na primavera de 1996. Foi feita uma comparação das concentrações dos ácidos carboxílicos entre dois sítios urbanos distintos. Os resultados demonstraram que os níveis de ácidos carboxílicos foram afetados pela variação sazonal no sítio com contribuição alta de emissão veicular enquanto que no outro sítio estudado não foi observada esta influência. As concentrações variaram de 0,64 a 11,8 ppbv para ácido fórmico e 0,51 a 10,7 ppbv para ácido acético. Os dados obtidos foram discutidos em relação à emissão direta e a produção fotoquímica in situ.

Ambient levels and diurnal profiles of formic and acetic acids were measured in the atmosphere of São Paulo City in winter and spring 1996. A comparison between two different urban sites was done. Results demonstrate that carboxylic acid levels were affected by seasonality in the site with high vehicular emission density, while no seasonal influence was observed for the other site studied. Ranges of mixing ratios from 0.64 to 11.8 ppbv for formic acid and 0.51 to 10.7 ppbv for acetic acid were recorded. The results concerning the carboxylic acid concentrations were discussed with respect to direct emission and in situ photochemical production.

Increasing attention is being paid to the use of biomarkers for determining the exposure of humans to air toxics. Biomarkers include the nonreacted toxic substance, their metabolites, or the reaction products of these toxics with naturally substances in the body. Significant progress has been made in the measurement of biomarkers during the past several years. Much of this progress has been because of the development of advanced analytical techniques for identification and quantification of the chemical species in complex matrix, such as biological fluids. The assessment of the potential cancer risk associated with exposure to benzene at occupational and non-occupational ambient is necessary because of the toxicological implications of this air pollutant. Thus, in this review, the analytical methodologies used to determine the benzene metabolites, in special, urinary muconic acid and S-phenylmercapturic acid, are described and several problems affecting the precision of these procedures are discussed. Finally, in view of the difficulty pointed out for selecting the more adequate biomarker, further studies to evaluate the human exposure levels to benzene should be done.

The presence of low carbonyl compounds (C1-C4) and glutaraldehyde was observed in 14 work-locations in São Paulo city, Brazil, during January to July 1997 period. The quantification of other carbonyls was not possible due to a sampling artifact caused probably by undesirable reactions between the ambient ozone and the organic substract of C18 cartridge used to collect carbonyls. High indoor concentrations, compared to outdoor levels, were observed for all compounds. Formaldehyde was the most abundant species (29 ppb) followed by acetone and acetaldehyde (25 and 17 ppb) with a small contribution of propanal, crotonaldehyde and C4 isomers (0.7 to 1.5 ppb) when related to the total indoor carbonyls level. Glutaraldehyde was observed only in two different occupational locations in a hospital at high concentrations (121 ppb). In general, high individual carbonyl levels as well as total carbonyls levels found in several locations indicated an unpropitious air quality for the occupants of these non-industrial sites.

In this work, analytical strategies are evaluated in order to measure accurately the ambient levels of atmospheric organic acids. Environmental considerations about the determination of low molecular weight mono- and di-carboxylic acids from urban areas of São Paulo are described.