RT Journal Article T1 Metal partitioning and speciation in a mining-impacted estuary by traditional and passive sampling methods A1 Ruiz Cánovas, Carlos A1 Basallote Sánchez, María Dolores A1 Borrego, Pedro A1 Millán Becerro, Ricardo A1 Pérez López, Rafael AB This study deals with the metal partitioning and bioavailability of metal/loids in the estuary Ria of Huelva (SW Spain) which is strongly affected by historical mining and industrial activities. To address this issue, traditional (i.e., grab samples) and passive sampling (i.e., diffusive gradient in thin films, DGTs) was carried out in the outer part of the estuary during different tidal cycles in order to determine the dissolved and particulate metal/loid concentrations. The dissolved concentrations exceeded, by several orders of magnitude, those reported in other estuaries worldwide that are affected by anthropogenic activities. A spatial pattern was observed in the metal distribution; a decrease seaward was recorded for some of the elements associated with mining (e.g., Cu, Zn, and Cd), the opposite tendency is observed for others associated with harbor emissions (e.g., Sn, Ni, or Pb). A different metal/loid partitioning pattern was also observed; Fe, and to a lesser extent Pb and Sn, were chiefly found in the particulate matter, while the rest of the elements were mainly found in the dissolved form. The bioavailability of the metal/loids was studied by speciation using both geochemical modeling and DGTs; while concentrations in DGTs supported metal/loid speciation for Zn, Cd, Mn, Co, As, and Sb according to their affinity to form strong or weak complexes, some discrepancies were observed for other elements such as Cu, V, Fe, and Pb, which are prone to forming strong complexes. The main reason behind the unexpectedly high Fe and Pb DGTs concentrations may be associated with their presence in the colloidal particles passing through the DGT. There was a strong positive correlation between dissolved and DGT concentrations for Cd and Mn, and to a lesser extent for Fe and Cu, highlighting the direct relationship between the concentrations in water and availability to living organisms in the estuary. PB Elsevier SN 1879-1026 (electrónico) SN 0048-9697 YR 2020 FD 2020-06-20 LK https://hdl.handle.net/10272/22927 UL https://hdl.handle.net/10272/22927 LA eng NO Cánovas, C. R., Basallote, M. D., Borrego, P., Millán-Becerro, R., & Pérez-López, R. (2020). Metal partitioning and speciation in a mining-impacted estuary by traditional and passive sampling methods. In Science of The Total Environment (Vol. 722, p. 137905). Elsevier BV. https://doi.org/10.1016/j.scitotenv.2020.137905 NO This work was supported by the Spanish Ministry of Economy and Competitiveness through the research project CAPOTE (CGL2017-86050-R) and by the CEIMAR Excellence Research Campus through the project CEIMAR-CEIJ-005. M.D. Basallote thanks the Spanish Ministry of Science and Innovation for the Postdoctoral Fellowship granted under application reference IJC2018-035056-I. The authors would also like to thank to the Co Editor-in-Chief Dr. Damiá Barceló and two anonymous reviewers for the support and comments that notably improved the quality of the original paper. DS Repositorio Institucional de la Universidad de Huelva RD 31 may 2026