Distribution and Role of Trace Transition Metals in Glycera Worm Jaws Studied with Synchrotron Microbeam Techniques

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Lichtenegger HC, Birkedal H, Casa DM, Cross JO, Heald SM, Waite JH, Stucky GD

Abstract:
A combination of position-resolved synchrotron microbeam techniques was used to explore the distribution and role of trace transition metals in the jaws of Glycera dibranchiata. The mandibles of this marine sediment worm have recently been found to be reinforced by the copper-based biomineral atacamite [Cu2(OH)3Cl]. Here we show that the system is more complex, containing zinc and iron and unmineralized copper compounds as well. X-ray absorption spectroscopy studies showed that a fraction of copper is present in oxidation state, Cu(I), in contrast to the mineral that exclusively contains Cu(II). X-ray fluorescence imaging revealed traces of copper also in the jaw base devoid of mineral. Traces of iron were found as well, but occurred spatially correlated with the copper mineral, suggesting a substitution of copper atoms by iron in the atacamite mineral. Zinc was evenly dispersed throughout the jaw matrix, quite in analogy to zinc in Nereis jaw, a related worm species, where nonmineralized zinc serves to cross-link and harden the proteinaceous matrix.