This study investigates the chemical complexity and toxicity of volatile organic compounds (VOCs) emitted from national petrochemical industrial parks and their effects on air quality in an industrial area of Nanjing, China. Field measurements were conducted from 1 December 2022, to 17 April 2023, focusing on VOC concentrations and speciations, diurnal variations, ozone formation potential (OFP), source identification, and associated health risks. The results revealed an average total VOC (TVOC) concentration of 15.9 ± 12.9 ppb and an average OFP of 90.1 ± 109.5 μg m−3. Alkanes constituted the largest fraction of VOCs, accounting for 44.1%, while alkenes emerged as the primary contributors to OFP, comprising 52.8%. TVOC concentrations peaked before dawn, a pattern attributed to early morning industrial activities and nighttime heavy vehicle operations. During periods classified as clean, when ozone levels were below 160 μg m−3, both TVOC (15.9 ± 12.9 ppb) and OFP (90.4 ± 110.0 μg m−3) concentrations were higher than those during polluted hours. The analysis identified the key sources of VOC emissions, including automobile exhaust, oil and gas evaporation, and industrial discharges, with additional potential pollution sources identified in adjacent regions. Health risk assessments indicated that acrolein exceeded the non-carcinogenic risk threshold at specific times. Moreover, trichloromethane, 1,3-butadiene, 1,2-dichloroethane, and benzene were found to surpass the acceptable lifetime carcinogenic risk level (1 × 10−6) during certain periods. These findings highlight the urgent need for enhanced monitoring and regulatory measures aimed at mitigating VOC emissions and protecting public health in industrial areas. In the context of complex air pollution in urban industrial areas, policymakers should focus on controlling industrial and vehicle emissions, which can not only reduce secondary pollution, but also inhibit the harm of toxic substances on human health.
