Development of Polydopamine–Chitosan-Modified Electrochemical Immunosensor for Sensitive Detection of 7,12-Dimethylbenzo[a]anthracene in Seawater

7,12-Dimethylbenzo[a]anthracene (DMBA-7,12), a highly toxic and environmentally persistent polycyclic aromatic hydrocarbon (PAH), poses significant threats to marine biodiversity and human health due to its bioaccumulation through the food chain. Conventional chromatographic methods, while achieving comparable detection limits, are hindered by the need for expensive instrumentation and prolonged analysis times, rendering them unsuitable for rapid on-site monitoring of DMBA-7,12 in marine environments. Therefore, the development of novel, efficient detection techniques is imperative. In this study, we have successfully developed an electrochemical immunosensor based on a polydopamine (PDA)–chitosan (CTs) composite interface to overcome existing technical limitations. PDA provides a robust scaffold for antibody immobilization due to its strong adhesive properties, while CTs enhances signal amplification and biocompatibility. The synergistic integration of these materials combines the high efficiency of electrochemical detection with the specificity of antigen–antibody recognition, enabling precise qualitative and quantitative analysis of the target analyte through monitoring changes in the electrochemical properties at the electrode surface. By systematically optimizing key experimental parameters, including buffer pH, probe concentration, and antibody loading, we have constructed the first electrochemical immunosensor for detecting DMBA-7,12 in seawater. The sensor achieved a detection limit as low as 0.42 ng/mL. In spiked seawater samples, the recovery rates ranged from 95.53% to 99.44%, with relative standard deviations (RSDs) ≤ 4.6%, demonstrating excellent accuracy and reliability. This innovative approach offers a cost-effective and efficient solution for the in situ rapid monitoring of trace carcinogens in marine environments, potentially advancing the field of marine pollutant detection technologies.