Liquid chromatography-mass spectrometry approaches for analysis of polychlorinated alkanes: a review

Polychlorinated alkanes (PCAs), the primary components of technical mixtures known as chlorinated paraffins (CPs), are complex and persistent pollutants of growing environmental and analytical concern. Their widespread use and toxicological properties, particularly those of short- and medium-chain PCAs (C 10–17 ), have prompted increased regulatory and scientific attention. This review provides a comprehensive overview of recent advances in the analysis of PCAs using liquid chromatography coupled with mass spectrometry (LC–MS), with emphasis on separation, ionization, and detection strategies. Key developments in stationary and mobile phase selection, gradient optimization, and the role of mobile phase additives in enhancing ionization are critically evaluated. Particular attention is paid to the challenges posed by the structural complexity of PCAs, including isomeric diversity and mass spectral interferences, and how they are addressed by high-resolution and tandem mass spectrometric techniques. Variability in instrumental response across carbon-chain lengths and chlorination degrees is also examined. The review highlights current methodological advancements and limitations, and outlines perspectives for improving analytical reliability.