Optimizing the iodide-adduct chemical ionization mass spectrometry (CIMS) quantitative method for toluene oxidation intermediates: experimental insights into functional-group differences

Abstract. Iodide-adduct time-of-flight chemical ionization mass spectrometry (I-CIMS) has been developed as a powerful tool for detecting the oxidation products of volatile organic compounds. However, the accurate quantification of species that do not have generic standards remains a challenge for I-CIMS application. To accurately quantify aromatic hydrocarbon oxidation intermediates, both quantitative and semi-quantitative methods for I-CIMS were established for intermediate species. The direct quantitative experimental results reveal a correlation between sensitivity to iodide addition and the number of polar functional groups (keto groups, hydroxyl groups, and acid groups) present in the species. Leveraging the selectivity of I-CIMS for species with diverse functional groups, this study established semi-quantitative equations for four distinct categories: monophenols, monoacids, polyphenol or diacid species, and species with multiple functional groups. The proposed classification method offers a pathway to enhancing the accuracy of the semi-quantitative approach, achieving an improvement in R2 values from 0.52 to beyond 0.88. Overall, the categorized semi-quantitative method was utilized to quantify intermediates formed during the oxidation of toluene under both low-NO and high-NO conditions, revealing the differential variations in oxidation products with varying levels of NOx concentration.