Information depths of analytical techniques assessing whitefish otolith chemistry

The elemental composition of otoliths provides historical information on migration and provenance of fish. Due to the complex structure of the otoliths, the depth from which the elemental information originates has to be considered. In this work, three analytical methods often used to assess otolith chemistry are compared. The information depths are calculated for µ-XRF and PIXE and measured for LA-ICP-MS. The information depth in PIXE depends on the energy of the incident particles and on the element to be analysed while in XRF it depends mostly on the element to be analysed as the energy of the incident X-rays usually is high enough to excite atoms at depths of several hundreds of micrometres. If we assume that the otolith is exposed to X-rays from a Rh-tube (20.16 keV) about 50% of the detectable Sr(Kα) X-rays will be emitted from a depth ranging from 0 to 114 µm. In the case of PIXE with 3 MeV protons the corresponding range is 0–15 µm. The information depths in LA-ICP-MS were determined by measuring the depth of the laser-ablated craters or trenches that remained on the otolith surface. The depths measured with a scanning white light interferometer (SWLI) were found to be about 40 µm (spots) and 11 µm (trenches).

The correlation between strontium concentrations obtained by spot analysis of whitefish otoliths with PIXE and LA-ICP-MS was excellent (92%), although different spot sizes were used. A comparison of strontium concentration profiles measured with µ-XRF and LA-ICP-MS showed that the higher information depth of µ-XRF in combination with the 52 degree angle of the incident X-rays smoothens out the sharp edges seen in the LA-ICP-MS profiles. Otoliths from whitefish captured in the Baltic Sea (n = 30) were analysed in this comparison of methods. Among these whitefish there are sea spawners, river spawners and stocked fish with different life history and different otolith chemistry.