Abstract
Heavy metals in agricultural systems pose a significant challenge to food security, especially in regions with long-term intensive land use. While the Pannonian Plain represents Croatia's primary breadbasket, accounting for a significant portion of the nation's cereal production, data on the soil-to-grain transfer of heavy metals and the associated human exposure risk are limited. The objective of this study was (i) to determine the concentrations of arsenic (As), cadmium (Cd), and lead (Pb) in agricultural soils and corresponding grains (wheat, barley, and maize) across four principal counties within the Pannonian region of Croatia; (ii) to evaluate the soil-to-grain transfer factors that varied regionally and among cereal types; and (iii) to assess the potential non-carcinogenic health risks for both adults and children highlighting differences in exposure due to body weight and consumption patterns. Soil and cereal grain samples were collected in 2019 and 2020, and metal concentrations were determined by ICP-MS after microwave acid digestion. The transfer of metals from soil to grain was estimated using the transfer factor (TF), while exposure assessment was conducted by calculating the estimated daily intake (EDI), hazard quotient (HQ), and hazard index (HI). Due to the nonlinear distribution of the data and the lack of strictly matched soil and grain samples, median metal concentrations pooled across all studied regions were used for exposure assessment. For As, a conservative approach was applied, assuming that 50% of the total As is in inorganic form. Additionally, a probabilistic risk assessment using Monte Carlo simulations was conducted to account for variability in body weight and cereal intake, providing a more comprehensive evaluation of potential exposure. The results showed differences in metal accumulation among cereal species, with wheat and barley tending to accumulate more Cd than maize, while As and Pb concentrations in grains were low for all crops studied. Although soil metal concentrations in Međimurje County were generally low, elevated TF values for As and Pb were observed, indicating enhanced soil-to-plant transfer under specific local soil conditions. In contrast, high soil metal concentrations in Slavonski Brod-Posavina County were associated with low TF values, suggesting limited bioavailability and restricted transfer to cereal grains. Both deterministic and probabilistic assessments indicated that the HQ and HI for adults and children were below 1, suggesting low non-carcinogenic risk from cereal consumption. These findings highlight pronounced regional and crop-specific differences in soil-to-plant metal transfer and confirm that low soil contamination does not necessarily imply low transfer potential, emphasizing the importance of integrated soil-plant-grain monitoring for food safety assessment.