Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater.

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL−1(0.05 µgL−1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL−1(<0.02 µgL−1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/zand 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL−1(0.5 µgL−1) to 25.0 ng/mL−1(25.0 µgL−1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL−1(0.5 µgL−1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca2+present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed. [ABSTRACT FROM AUTHOR]