Elevated manganese concentrations at the cores of clupeid otoliths: possible environmental,physiological, or structural origins

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to investigate the distribution of manganese (Mn) in Atlantic herring (Clupea harengus L.) otoliths. An unusual pattern of Mn concentration, which has not previously been reported in fish otoliths, was observed. Time-resolved plots (time roughly equivalent to ablation depth) of the Mn signal recorded in the ICP-MS detector during ablation of otoliths contained a distinct peak, suggesting that elevated Mn concentrations were specific to certain regions. Ablation inside and outside of the otolith core revealed that the region of high Mn concentration coincided with the ablation of the core. It was initially suggested that Mn from the gravel substrate on which herring eggs are incubated is incorporated into the otolith core, producing elevated Mn concentrations in this region. It was hypothesised that otoliths from fish whose eggs are not incubated in gravel will not contain high Mn concentrations at the core. To test this, otoliths of sprat (Sprattus sprattus), which have a pelagic embryological stage, and from reared herring, which were incubated on glass plates, were analysed using LA-ICP-MS. Peaks in the Mn signal were observed during the ablation of cores from some sprat and reared herring otoliths, indicating that incubation on a gravel substrate is not necessary for the accumulation of Mn at the otolith core and that otoliths from both pelagic and demersally spawning fish species can contain elevated Mn concentrations. The results suggest that Mn concentrations at the otolith core do not reflect the external environment of the developing embryo. Two other hypotheses are considered. A dramatic increase in Mn concentrations in the egg, associated with embryological development, may produce elevated Mn levels at the otolith core. Alternatively, the high levels of Mn observed at the otolith core may reflect spatial variation in the crystal structure of the calcium carbonate portion of the otolith. The possible influence of physiological or structural factors on the chemical composition of the otolith core may confound the environmental signal in this region of the otolith. This has important implications for the interpretation of otolith chemistry data.Communicated by J.P. Thorpe, Port Erin