Elemental fingerprinting of thornback ray (Raja clavata) muscle tissue as a tracer for provenance and food safety assessment

The verification of food authenticity and provenance is a complex task and has raised public concern in recent years due to multiple episodes of food fraud and potential risks to consumers. In this sense, the evaluation of multi-elemental signatures is increasingly applied to confirm and validate the site of origin of animal products. Yet, we lack understanding of its efficacy for mobile organisms such as fish. Using multi-element Total Reflection X-ray Fluorescence (TXRF) analysis of muscle of thornback ray Raja clavata we successfully identified the fishing area of individuals collected in four areas along the Portuguese Atlantic coast (Atlantic Iberian waters, Northeast Atlantic). Overall, As, Fe, Sn, V and Zn presented higher contributions to discrimination (especially Fe and Rb for neighbouring collection areas), whilst the higher concentration elements (Na, K, P, S, Ca, Cl, Br and Sr) had similar concentrations among locations. Rays captured in the two areas with higher urbanization/industrialization presented higher concentration of elements associated with anthropogenic activities (such as As, Zn, Sn and V). In terms of food safety, only 0.9% and 2.8% of the individuals surpassed the recommended thresholds values for human consumption for Hg and Cd respectively. A canonical analysis of principal components resulted in classification accuracy of thornback ray to collection site of 56.7–84.2% (depending on site), with an overall accuracy of 65.1% over c. 500 km of coast in the Northeast Atlantic.