Rapid On-Field Monitoring for Odor-Active Homologous Aliphatic Aldehydes and Ketones from Hot-Mix Asphalt Emission via Dynamic-SPME Air Sampling with Online Gas Chromatographic Analysis

Odorous emissions from hot-mix asphalt (HMA) plants are a growing environmental concern, particularly due to airborne aldehydes and ketones, which have low odor thresholds and a strong sensory impact. This study presents a field-ready analytical method for monitoring odor-active volatile compounds. The system uses dynamic solid-phase microextraction (SPME and SPME Arrow) with on-fiber derivatization via O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and is coupled to gas chromatography-mass spectrometry (GC-MS) for direct detection. A flow-cell sampling unit enables the real-time capture of aliphatic aldehydes and ketones under transient emission conditions. Calibration using permeation tubes demonstrated sensitivity (limits of detection (LODs) below 0.13 μg/m³), recovery above 85% and consistent reproducibility. Compound identity was confirmed using retention indices and fragmentation patterns. Uncertainty assessment followed ISO GUM (Guide to the Expression of Uncertainty in Measurement) standards, thereby validating the method's environmental applicability. Field deployment 200 m from an HMA facility identified measurable concentrations that aligned with CALPUFF model predictions. The method's dual-isomer resolution and 10 min runtime make it ideal for responding to time-sensitive odor complaints. Overall, this approach supports regulatory efforts by enabling high-throughput on-site chemical monitoring and improving source attribution in cases of odor nuisance.