Detection of Volatile Toxic Industrial Chemicals with Classical Ion Mobility Spectrometry and High-Kinetic Energy Ion Mobility Spectrometry.

Due to their high sensitivity and compact design, ion mobility spectrometers are widely used to detect toxic industrial chemicals (TICs) in air. However, when analyzing complex gas mixtures, classical ion mobility spectrometry (IMS) suffers from false-positive rates due to limited resolving power or false-negative rates caused by competitive ion-molecule reactions and the resulting suppression of certain analyte ions. To overcome these limitations, high-kinetic energy IMS (HiKE-IMS) was introduced some years ago. In contrast to classical IMS, HiKE-IMS is operated at decreased pressures of 20···60 mbar and high reduced electric field strengths / of up to 120 Td. Under these conditions, the influence of competitive ion-molecule reactions on the prevailing ion population should be less pronounced, thus reducing false negatives. Additionally, effects such as fragmentation and field-dependent ion mobility may help to reduce false positives. In this work, the capabilities and limitations of HiKE-IMS in the field of on-site detection of the volatile TICs NH, HCN, HS, HCl, NO, Cl, and SO are evaluated for the first time. Based on the limits of detection and the extent of spectral and chemical cross-sensitivities in gas mixtures, the results obtained for HiKE-IMS are compared with those obtained for classical IMS. It is shown that HiKE-IMS is less sensitive in comparison to classical IMS. However, when used for TIC detection, the reduced sensitivity of HiKE-IMS is not a major drawback. With values around 1 ppm, the achievable limits of detection for almost all TICs are below the AEGL-2 (4h) levels. Furthermore, in comparison to classical IMS, it is still striking that HiKE-IMS shows significantly less spectral and chemical cross-sensitivities and thus exhibits considerably lower false-positive and false-negative rates. Overall, it thus turns out that HiKE-IMS is a promising alternative to classical IMS in the field of on-site detection of TICs.