Automated method for volatile fatty acids determination in anaerobic processes using in-syringe magnetic stirring assisted dispersive liquid-liquid microextraction and gas chromatography with flame ionization detector

Abstract

Volatile fatty acids (VFAs) are key parameters to monitor anaerobic digestion processes. Thus, a fast, simple and precise determination of these analytes is necessary for a timely characterization of the biological processes present in municipal solid waste and wastewater treatment plants. In this work, an automated method for the extraction and preconcentration of VFAs, based on dispersive liquid-liquid microextraction with magnetic stirring in syringe, and gas chromatography with flame ionization detector for the separation and detection, is described. The effect of parameters such as the type and volume of extraction solvent, pH, salting out effect and stirring time, was studied using a multivariate and univariate experimental design. Extraction and preconcentration were performed simultaneously using tert-butyl methyl ether (TBME) as the extraction solvent, after stirring 100 s at a constant rate. The detection limits were in the range of 0.1 - 1.3 mg L−1 and a good linearity was observed up to 1000 mg L−1 of the studied VFAs, with a range of R2 between 0.9997 and 0.9999. The intra and interday precision expressed as relative standard deviation (n= 5) varied between 0.7 and 2.4% and between 1.7 and 7.0%, respectively. Subsequently, the developed method was successfully applied to evaluate the presence of VFAs in wastewater samples from anaerobic treatments and an average relative recovery of 102% was obtained.