A preliminary study of iron isotope fractionation in marine invertebrates (chitons, Mollusca) in near-shore environments

Abstract. Chitons (Mollusca) are marine invertebrates that produce radulae (teeth or rasping tongues) containing high concentrations of biomineralized magnetite and other iron-bearing minerals. As Fe isotope signatures are influenced by redox processes and biological fractionation, Fe isotopes in chiton radulae might be expected to provide an effective tracer of ambient oceanic conditions and biogeochemical cycling. Here, in a pilot study to measure Fe isotopes in marine invertebrates, we examine Fe isotopes in modern marine chiton radulae collected from different locations in the Atlantic and Pacific oceans to assess the range of isotopic values, and to test whether or not the isotopic signatures reflect seawater values.

Values of δ⁵⁶Fe (relative to IRMM-014) in chiton teeth range from −1.90 to 0.00 ‰ (±0.05‰ (2σ) uncertainty in δ⁵⁶Fe), probably reflecting a combination of geographical control and biological fractionation processes. Comparison with published local surface seawater Fe isotope data shows a consistent negative offset of chiton teeth Fe isotope compositions relative to seawater. Strikingly, two different species from the same locality in the North Pacific (Puget Sound, Washington, USA) have distinct isotopic signatures. Tonicella lineata, which feeds on red algae in the sublittoral zone, has a mean δ⁵⁶Fe of −0.65 ± 0.26‰ (2σ, 3 specimens), while Mopalia muscosa, which feeds on both green and red algae in the eulittoral zone, shows lighter isotopic values with a mean δ⁵⁶Fe of −1.47 ± 0.98‰ (2σ, 5 specimens). Three possible pathways are proposed to account for the different isotopic signatures: (i) physiologically controlled processes within the chitons that lead to species-dependent fractionation; (ii) diet-controlled variability due to different Fe isotope fractionation in the red and green algal food sources; and (iii) environmentally controlled fractionation that causes variation in the isotopic signatures of bioavailable Fe in the different tidal regions. Our preliminary results suggest that while chitons are not simple recorders of the ambient seawater Fe isotopic signature, Fe isotopes provide valuable information concerning Fe biogeochemical cycling in near-shore environments, and may potentially be used to probe sources of Fe recorded in different organisms.