Accurate and stable detection of p-phenylenediamine antioxidants and their transformation products in aquatic products using antioxidant protection – Analysis of actual aquatic products

Given the high toxicity of N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD) derivatives, such as 6PPD quinone (6PPDQ) to salmon, as well as their ubiquitous presence in the environment, the contaminant of aquatic food products has drawn significant attention. However, analytical methods for p-Phenylenediamines (PPDs) and their transformation products (TPs) in aquatic products remain underdeveloped. In particular, the degradation of some compounds and strong matrix effects complicate detection. In this study, we present a stable, rapid, and sensitive method combining salt-out assisted extraction, antioxidant protection, and multi-plug filtration clean-up (m-PFC) to detect two PPDs and five TPs in aquatic products. Crucially, the appropriate selection of antioxidants prevented the degradation of the easily oxidized target compounds. Further, the m-PFC method significantly enhanced the purification efficiency, achieving satisfactory recoveries (62.1–115 %), and method detection limits (MDLs) ranging from 0.00300 to 0.400 μg/kg. Subsequently, the method was applied to monitor PPDs and their TPs in aquatic products systematically, revealing the presence of 6PPD and N-isopropyl-N′-phenyl-1,4-phenylenediamine (IPPD) in white shrimp from aquafarms, whereas none of the seven target analytes were detected in fish and crab samples. These findings contribute to the detection of PPDs, their TPs and other unstable chemicals in aquatic products, thereby providing insights into their concentrations in these products. [Display omitted] •An efficient and stable method for the detection of PPDs and their TPs was developed.•Oxidative degradation is the main cause of low extraction efficiency of PPDs and some TPs.•Combined strong antioxidant protection for stable extraction PPDs and their TPs was first proposed.•A multi-plug filtration cleanup column for rapid purification was established.•6PPD and IPPD were detected in white shrimp samples collected from aquafarms.