Title : Human health risks associated with dietary intake of ionic and nanoparticulated copper oxide from the Spanish Northwestern coast marine-origin food
Abstract:
Bioaccumulation of metals and their nanoparticles in marine organisms becomes an emerging concern, addressed in this study by a multidisciplinary approach integrating elemental and nanoparticulated analyses, bioaccumulation studies and health risk assessment. Conventional ICP-MS was used to assess total copper in diverse seafood samples from two different geographical Spanish coast areas, including six molluscs species, two edible seaweeds and processed seafood samples, which ranged from 0.22 to 14.2 mg kg-1. On the other hand, single particle inductively coupled plasma mass spectrometry (sp-ICP-MS) was used as a fitted analytical tool for characterization of copper oxide nanoparticles (CuONPs), with concentrations ranging from 2.7 × 108 to 1.0 × 109 part kg-1 and mean particle sizes between 26 and 38 nm. Suitable isolation of CuONPs from samples was performed by an enzymatic ultrasound-assisted extraction optimised via Response Surface Methodology (RSM) analysis, to maximize both the extracted CuONPs mass and number concentrations without altering their native size and morphology. Selected extraction conditions involved ultrasonication for 8 minutes at 62% amplitude in continuous mode, employing a pancreatin/lipase mixture solution (2.9 g L-1).
Findings provide alarming bioaccumulation evidence of ionic Cu and CuONPs in marine organisms, with concentrations exceeding the seawaters levels found in their fishing zones. Thus, health risks associated with bioaccumulation events through seafood ingestion were evaluated upon monitoring hazard parameters like Estimated Daily Intakes (EDIs), Target Hazard Quotients (THQs), and Maximum Allowable Consumption Rates (CRlim and CRmm). This health risks study has considered four hazard scenarios for each target attending diverse seafood consumption levels and potential health conditions associated with Cu elimination such as Wilson's disease. EDI, THQ and CR limits regarding ionic Cu suggest the intake of certain seafood samples (oysters) and even the cumulative seafood intake could pose health risks under specific scenarios. In contrast, CuONPs ingestion from seafood appears to be initially safe, based on THQ and CR values, although it must be aware about the existence of a meaningful research gap regarding oral reference doses from official regulatory agencies for these emerging pollutants. Then, the implementation of such integrated methodologies becomes essential to support informed risk management decisions and to guide the development of regulatory measures aimed at minimizing environmental-food contamination and protecting human health in the long term.

