Overcoming matrix effects in quantitative liquid chromatography-mass spectrometry analysis of steroid hormones in...

Accurate and reliable measurements are mandatory in the field of environmental monitoring. Matrix effects are often depicted as the Achilles' heel of liquid chromatography-mass spectrometry analysis since they may be prejudicial for analytical performances such as detection capability and accuracy, if not documented or compensated. Here a methodology for the evaluation and compensation of matrix effects is described.

Natural and synthetic representative water samples were used for the evaluation of matrix effects with the post-extraction addition technique. Samples were analysed using ultra-performance liquid chromatography separation coupled to tandem mass spectrometry and electrospray ionization. Isotopic dilution was investigated as a way to allow compensation of signal alteration and therefore satisfactory quantification. When this approach was not possible, a methodology was conducted for choosing the most appropriate internal standard.

The matrix effects were dependent on both matrix composition and nature of analyte. They ranged from total signal suppression to signal enhancement of +27% but were independent of compound concentration. The correction of matrix effects by internal standards was satisfactory, particularly for compounds benefiting from isotope dilution leading to acceptable quantification performances.

Even if no exhaustive or agreed criteria exist for the final interpretation of matrix effects, this study highlights the interest in isotope dilution for reducing their inherent prejudicial effects in quantification and the need to conduct this type of study for representative matrices. Moreover, a methodological approach is proposed for choosing the most appropriate available internal standard when isotope dilution is not possible.