Summary1. Trace element concentrations in fish earstones ('otoliths') are widely used to discriminate spatially discrete populations or individuals of marine fish, based on a commonly held assumption that physiological influences on otolith composition are minor, and thus variations in otolith elemental chemistry primarily reflect changes in ambient water chemistry. 2. We carried out a long-term (1-year) experiment, serially sampling seawater, blood plasma and otoliths of mature and immature European plaice (Pleuronectes platessa L.) to test relationships between otolith chemistry and environmental and physiological variables. 3. Seasonal variations in otolith elemental composition did not track seawater concentrations, but instead reflected physiological controls on metal transport and biokinetics, which are likely moderated by ambient temperature. The influence of physiological factors on otolith composition was particularly evident in Sr/Ca ratios, the most widely used elemental marker in applied otolith microchemistry studies. Reproduction also triggered specific variations in otolith and blood plasma metal chemistry, especially Zn/Ca ratios in female fish, which could potentially serve as retrospective spawning indicators. 4. The influence of physiology on the trace metal composition of otoliths may explain the success of microchemical stock discrimination in relatively homogenous marine environments, but could complicate alternative uses for trace element compositions in biominerals of higher organisms.

Otolith microchemistry can provide valuable information about stock structure and mixing patterns when the magnitude of environmental differences among areas is greater than the cumulative influence of any vital effects. Here, the current understanding of the underlying mechanisms governing element incorporation into the otolith is reviewed. Hard and soft acid and base (HSAB) theory is employed to explore the differences in chemical behaviours, distributions and affinities between elements. Hard acid cations (e.g. Mg(2+) , Li(+) and Ba(2+) ) tend to be less physiologically influenced and accepted more readily into the otolith crystal lattice but are relatively homogeneous in seawater. Soft acid cations (e.g. Zn(2+) and Cu(2+) ) on the other hand, exhibit more varied distributions in seawater, but are more likely to be bound to blood proteins and less available for uptake into the otolith. The factors influencing the geographical distribution of elements in the sea, and their incorporation into the otoliths of marine fishes are reviewed. Particular emphasis is placed on examining physiological processes, including gonad development, on the uptake of elements commonly used in population studies, notably Sr. Finally, case studies are presented that either directly or indirectly compare population structuring or movements inferred by otolith elemental fingerprints with the patterns indicated by additional, alternative proxies. The main obstacle currently limiting the application of otolith elemental microchemistry to infer movements of marine fishes appears to lie in the largely homogeneous distribution of those elements most reliably measured in the otolith. Evolving technologies will improve the discriminatory power of otolith chemistry by allowing measurement of spatially explicit, low level elements; however, for the time being, the combination of otolith minor and trace element fingerprints with alternative proxies and stable isotopic ratios can greatly extend the scope of migration studies. Among the otolith elements that routinely occur above instrument detection limits, Ba, Mn and Li were deemed the most likely to prove reliable geographic markers in marine species.

Please note that this is an author-produced PDF of an article accepted for publication following peer review. The definitive publisher-authenticated version is available on the publisher Web site.physiological (ontogeny and growth) histories. A consistent temperature response was not evident across studies for either environmental or physiological tracers, presumably attributable to variable relationships between temperature and fish behavior and physiology (e.g., feeding rate, reproduction). Biomineralization thus has a controlling effect on otolith element concentrations for elements that are linked with somatic growth, but not for elements that substitute for Ca in the crystal lattice. Interpretation of the ecological significance of patterns from field samples therefore needs to consider the impact of the underlying biomineralization processes of the element in question as well as physiological processes regulating the availability of ions for inclusion in the growing crystal lattice. Such understanding will enhance the utility of this technique to address fisheries management questions.