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Zinc incorporation in marine bivalve shells grown in mine-polluted seabed sediments: a case study in the Malfidano mining area (SW Sardinia, Italy)

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Abstract

Zinc incorporation into marine bivalve shells belonging to different genera (Donax, Glycymeris, Lentidium, and Chamelea) grown in mine-polluted seabed sediments (Zn up to 1% w/w) was investigated using x-ray diffraction (XRD), chemical analysis, soft x-ray microscopy combined with low-energy x-ray fluorescence (XRF) mapping, x-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). These bivalves grew their shells, producing aragonite as the main biomineral and they were able to incorporate up to 2.0–80 mg/kg of Zn, 5.4–60 mg/kg of Fe and 0.5–4.5 mg/kg of Mn. X-ray absorption near edge structure (XANES) analysis revealed that for all the investigated genera, Zn occurred as independent Zn mineral phases, i.e., it was not incorporated or adsorbed into the aragonitic lattice. Overall, our results indicated that Zn coordination environment depends on the amount of incorporated Zn. Zn phosphate was the most abundant species in Donax and Lentidium genera, whereas, Chamelea shells, characterized by the highest Zn concentrations, showed the prevalence of Zn-cysteine species (up to 56% of total speciation). Other Zn coordination species found in the investigated samples were Zn hydrate carbonate (hydrozincite) and Zn phosphate. On the basis of the coordination environments, it was deduced that bivalves have developed different biogeochemical mechanisms to regulate Zn content and its chemical speciation and that cysteine plays an important role as an active part of detoxification mechanism. This work represents a step forward for understanding bivalve biomineralization and its significance for environmental monitoring and paleoreconstruction.

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Acknowledgments

The authors acknowledge the CERIC-ERIC Consortium (grant numbers: 20152041, 20162061, 20167045) for the access to experimental facilities and financial support and the Romanian Ministry of Education (through the Core Program, Project PN16-480102). XAFS (Elettra) 20160254 beamtime, Diamond SP 16496 beamtime, and grant are acknowledged. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. GDG and DM acknowledge RAS (grant number: E58C16000080003) and RAS/FBS (grant number: F72F16003080002). The Grant of Excellence Departments, MIUR (ARTICOLO 1, COMMI 314–337 LEGGE 232/2016), is gratefully acknowledged. We also thank three anonymous Journal Reviewers for their excellent constructive comments.

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Medas, D., Carlomagno, I., Meneghini, C. et al. Zinc incorporation in marine bivalve shells grown in mine-polluted seabed sediments: a case study in the Malfidano mining area (SW Sardinia, Italy). Environ Sci Pollut Res 25, 36645–36660 (2018). https://doi.org/10.1007/s11356-018-3504-y

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