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Optimization of an ultrasound-assisted derivatization for GC/MS analysis of oxygenated organic species in atmospheric aerosol

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Abstract

A novel ultrasound-assisted derivatization followed by GC/MS analysis was developed for the quantification of oxygenated organic species in ambient aerosol. Derivatization parameters mostly influencing the analytical response were investigated, i.e., solvent type, reagent concentration, and reaction duration. Response surface methodology was used to design experiments and a quadratic model was utilized to predict the variables and establish the optimal conditions. The study was performed on standard solutions of 30 compounds representing the major classes of oxygenated compounds typically found in ambient aerosol, i.e., low molecular weight carboxylic acids, sugars, and phenols. In comparison with conventional methods, the optimized procedure uses mild reaction temperature (room temperature instead of 70 °C), reduces the amount of silyl reagent (24 vs. 40 μL), and shortens derivatization times (45 vs. 70 min), participating in the current trend of analytical chemistry towards clean, green methods that reduce costs and decrease pollution. Once optimized, the ultrasound procedure was validated by assessing for repeatability, linearity, detection limits, and derivative stability. For all oxygenated organic species, the proposed method showed a good reproducibility—as the relative standard deviations (RSDs%, n = 5) of intra-day analysis were ≤7% — a good linearity with the correlation coefficients of calibration curves R 2 ≥ 99.8, and low detection limits, ranging from 0.34 to 6.50 ng μL−1; thus it is suitable for its applicability in air quality monitoring. Finally, this method was successfully applied to determine 30 oxygenated organic species in three ambient PM2.5 samples collected at an urban site in Northern Italy in three different seasons.

Ultrasound-assisted derivatization is a green alternative method for GC/MS analysis of oxygenated organic species in atmospheric aerosol towards reduction of energy and reactive consumption.

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Acknowledgements

Eugenia Villaverde-de-Sáa acknowledges the Spanish Ministry of Economy and Competitiveness (Ministerio de Economía y Competitividad, MINECO) for her doctoral (FPI) and research stay grants.

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Authors and Affiliations

  1. Department of Chemical and Pharmaceutical Sciences, University of Ferrara, Via Fossato di Mortara 17/19, 44100, Ferrara, Italy

    Maria Chiara Pietrogrande, Francesco Manarini & Marco Visentin

  2. IIAA - Institute of Food Analysis and Research, Department of Analytical Chemistry, University of Santiago de Compostela, R/Constantino Candeira S/N, 15782, Santiago de Compostela, Spain

    José Benito Quintana, Rosario Rodil & Eugenia Villaverde-de-Sáa

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  1. Maria Chiara Pietrogrande
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Correspondence to Maria Chiara Pietrogrande.

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Pietrogrande, M.C., Manarini, F., Quintana, J.B. et al. Optimization of an ultrasound-assisted derivatization for GC/MS analysis of oxygenated organic species in atmospheric aerosol. Anal Bioanal Chem 409, 4279–4291 (2017). https://doi.org/10.1007/s00216-017-0379-6

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