Signal correction using molecular species to improve biodiesel analysis by microwave-induced plasma optical emission spectrometry

Microwave-induced plasma optical emission spectrometry (MIP OES) and a simple dilute-and-shoot sample preparation procedure with 1-propanol are used to determine Ca, K, Mg and Na in biodiesel fuel. MIP naturally occurring molecular species are used to probe plasma condition variations during sample introduction, and then correct analytical signals to improve accuracies. The electronic transitions for N-2(+)(0-0, B-2 Sigma(+)(u) -> X-2 Sigma(+)(g)) and OH (0-0, A(2)Sigma(+) -> X-2 pi(i)) are used as molecular probes. A biodiesel standard reference sample is analyzed and the results for the molecular probe signal correction method are compared with values obtained with a traditional external standard calibration (EC). Improved accuracies were observed for Ca using the N-2(+) probe, and for K, Mg and Na using OH. Recoveries were in the 82-104% range for all analytes (60-130% for EC). The limits of detection (LODs) for Ca, K, Mg and Na are 70, 7, 9 and 8 mu g/L, respectively (2 mg/kg for Ca, and 0.2 mg/kg for all the other analytes). The method was applied to three biodiesel fuel samples and the concentrations ranges for Ca, K and Na were 9.0-16.0,10.6-142.1, and 7.8-52.7 mg/kg, respectively. Magnesium values were lower than the LOD in all cases. Analytical signal correction using plasma naturally occurring molecular species has the potential to significantly improve accuracy and sample throughput. It allows for effective determinations without the need for time-consuming calibration methods such as standard additions. (C) 2016 Elsevier B.V. All rights reserved.