Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric particulate matter

Abstract

Abstract. A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter is presented. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. Particulate matter was collected on quartz fibre filters using dichotomous high volume air samplers. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography and solid phase extraction. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyl)trifluoroacetamide, was added for Gas Chromatography-Mass Spectrometry analysis. The second half of the sample was stored in a refrigerator. For samples with concentrations exceeding 1 ng μl−1, the second half of the sample was used for measurement of stable carbon isotope ratios by Gas Chromatography-Isotope Ratio Mass Spectrometry. The procedure described in this paper provides a method for the analysis of methylnitrophenols in atmospheric particulate matter at concentrations as low as 0.3 pg m−3 and for stable isotope ratios with an accuracy of better than ±0.5‰ for concentrations exceeding 100 pg m−3. In all atmospheric particulate matter samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol, with concentrations ranging from the low pg m−3 range in rural areas to more than 200 pg m−3 in some samples from a suburban location.