Significance of otolith calcium carbonate crystal structure diversity to microchemistry studies

Otoliths, calcium carbonate (CaCO3) ear stones of fish, contain a wealth of information about fish life and environmental history yet the CaCO3 polymorph form the otolith is made of is a critical, but seldom considered, piece of information during otolith analysis. Otolith trace element chemistry data increasingly informs management decisions, but recent work has shown that CaCO3 polymorphs-aragonite, vaterite, and calcite-can bear on incorporation of trace elements in a non-trivial way. Most fishes are thought to have otoliths of the aragonite CaCO3 form, but this construct is potentially outdated with many recent literature reports showing otherwise. Our study used previously unpublished neutron diffraction data and reports from published literature to address three objectives: (1) summarize the relative effects of otolith CaCO3 polymorphism on otolith microchemistry, (2) summarize reports of otolith polymorphs to gain a better understanding of the extent of non-aragonite otoliths among fishes, (3) outline future research needed to align interpretations of microchemistry with our current understanding of otolith polymorph diversity. We found that while aragonite otoliths are the most common, so are exceptions. For example, the ostensibly rare (among species) CaCO3 form vaterite was reported in at least some otoliths of 40% of the species surveyed. Our work suggests that examination of the CaCO3 polymorph composition of otoliths should become more common particularly in studies where results will or may be used to inform management decisions. Future research should work to attribute controls on otolith CaCO3 polymorph expression using a combination of -omics and material characterization approaches to enrich the life history and environmental information output from otoliths and increase our understanding of the assumptions made in otolith trace element chemistry studies.