A simplified method for determination of short-, medium-, and long-chain chlorinated paraffins using tetramethyl ammonium chloride as mobile phase modifier.

The formation of halide adducts ion is an important pathway to improve the sensitivity of analytes in liquid chromatography (LC) combined with negative electrospray ionization (ESI) mass spectrometry (MS). Although adding modifier in mobile phase is generally the simplest way to form anions adducts, the formation of halide adducts ion requires a complex post-column addition strategy since traditional halide ionization enhancement reagents are incompatible with LC systems. To solve this problem, the volatile organochlorine salt tetramethyl ammonium chloride (TMAC) was therefore investigated as a potentially non-corrosive mobile phase modifier that was confirmed to be compatible with both LC and MS systems in this study. When short-chain, medium-chain, and long-chain chlorinated paraffins (CPs) were determinated simultaneously by ultra-high performance LC combined with ESI high resolution MS (UPLC-ESI-HRMS), all of them tended to ionize by forming [M+Cl] ions and exhibited excellent sensitivity with the instrumental detection limits of 1-4 pg/μL. Meanwhile, their sensitivities towards CPs were less dependent on their Cl content with the total relative response factors of 0.8-3.5. The method's utility was demonstrated through determination of CPs in surface soil and chicken muscle samples. This was an effective and practical method to enhance the selectivity for [M + Cl] ions and improve sensitivity towards CPs with various carbon lengths. Importantly, post-column addition was not required, and thus the analytical procedure was simplified. The method has also improved sensitivity towards some other organohalides and may be generally useful in the determination of challenging organic analytes.