Evaluating and Refining PCB Mixture Indicators in Marine Fish Through Explainable Artificial Intelligence

Polychlorinated biphenyls (PCBs) remain a major concern in marine ecosystems, where bioaccumulation in fish occurs as complex congener mixtures whose dynamics challenge conventional indicator approaches. This study develops and evaluates a data-driven framework for refining mixture-based indicators of PCB contamination by integrating ensemble machine learning with explainable artificial intelligence. Focusing on PCB-138 as a target indicator of cumulative PCB burden, we analyse concentrations of 24 organochlorines together with biological covariates in four Mediterranean edible pelagic fish species (sardine, anchovy, horse mackerel, and chub mackerel). Comparative evaluation of indicator performance shows that alternative congener combinations, including i4 PCBs (-138, -153, -170, -180), i6 PCBs (-138, -153, -170, -180, -118, -123), and mixtures incorporating DDD and DDE, more effectively represent total PCB burden than traditional indicator groups. Clustering identifies two distinct bioaccumulation settings, characterized by high-concentration coherent congener effects and low-concentration heterogeneous responses, demonstrating that indicator performance depends on concentration range and mixture context. The study illustrates how interpretable machine learning approaches can serve as formal tools for indicator evaluation and optimisation, strengthening long-term monitoring and management of legacy contaminants in marine ecosystems, particularly under conditions of persistent exposure and renewed inputs from sediment remobilization and riverine transport.