In situ analysis of trace elements and isotope ratios in fish otoliths using laser ablation sector field inductively coupled plasma mass spectrometry

Abstract

We applied laser ablation sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) to the analysis of trace element and isotopic signatures in fish otoliths. Manganese, Sr, and Ba profiles across juvenile Atlantic croaker (Micropogonias undulatus) otoliths, expressed as ratios to Ca, showed considerable spatial and temporal variations that were presumably reflective of variations in water chemistry over the same scales. Differences in otolith Mn:Ca ratios between adjacent rivers in Pamlico Sound, North Carolina, may be related to dissolved oxygen levels in the rivers through reductive release of Mn2+ from sediments. Strontium and Ba profiles appeared to accurately reflect differences in dissolved Sr and Ba in freshwater end-members, both between Pamlico Sound and Chesapeake Bay and between seasons within Chesapeake Bay. High-precision analyses of Sr:Ca ratios in a black drum (Pogonias cromis) otolith showed distinctive quasi-sinusoidal cycles that were correlated with validated annual bands. Analyses of Sr and Pb isotopes, in otoliths and standard reference material, respectively, found that SF-ICP-MS produced accurate and precise estimates of isotope ratios in both solution-based and laser ablation assays.