High resolution micromill sampling for analysis of fish otoliths by ICP-MS: effects of sampling and specimen preparation on trace element fingerprints.

Otoliths are calcified structures in the head of fish that record environmental information about fish's life history. Gathering the elemental information from the core of an otolith corresponding to the juvenile period of fish's life is critical to discriminate the adult fish to their natal habitats reliably. A high resolution micromill has been used to isolate the otolith core from a whole otolith for elemental analysis. The effects of micromilling procedures (e.g., sectioning, embedding and drilling) on contamination to otolith trace element levels were examined using paired blackfin tuna (Thunnus atlanticus) otoliths. Otoliths were decontaminated by dilute hydrogen peroxide and nitric acid throughout to remove surface contamination. A preconcentration procedure was used to determine the trace elements from the small core material by ICP-MS. It was found that micromilling procedures introduce significant contamination to otoliths, especially for Al, Cu, Pb and Zn. The sectioning procedure caused significant contamination for Co and Cu, while the embedding procedure resulted in contamination for nearly all trace elements (Al, Cd, Co, Cu, Ga, Mn, Ni, Pb, V and Zn). The combined sectioning, embedding and drilling procedure also resulted in contamination for most trace elements. Despite the contamination across all procedural steps, the decontamination procedure effectively removed the surface contamination with the exception of Pb and Zn. Bias (e.g., residual contamination) on Pb was small in comparison to overall concentration of Pb expected to occur in fish otoliths, therefore, its effect may be minor in discriminating individuals. Bias on Zn was larger that could limit its application in discriminating individuals.