The calculated difference between pKa values in H2O and D2O is in excellent agreement with experiment.

The strontium (Sr) and barium (Ba) profiles in otoliths of juvenile sockeye salmon Oncorhynchus nerka from British Columbia are measured using a Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) system and analyzed. The highest possible measurement resolution (near-daily) was used to assess variability and repeatability of the breakpoint (marine entry) estimates inferred from Sr:Ca and Ba:Ca ratios. Such resolution for the otolith chemical composition (to an accuracy of 2 μm) was reached using the rotating slit, which width was close to the daily circulus width of the otoliths. So, daily or 2-day changes in the elemental composition were recorded during the period of transition to the marine environment. Sr profiles were generally similar among the fish, starting with low values of Sr:Ca in the fresh water and increasing sharply after the marine entry. The Ba:Ca signal was more complex, showing in most cases a dramatic increase immediately before the breakpoint. Besides, multiple peaks in the Ba profiles were recorded prior to the marine transition with a significant difference of their number between fish from different populations. A breakpoint was detectable in the Ba profiles 3–11 µm prior to its appearance in the Sr profiles. The complexity of Ba profiles may cause erroneous estimates of the marine entry date; thus, the Sr signal is a more reliable marker of marine transition for juvenile sockeye.

The shift in strontium (Sr) concentrations in fish otoliths is a commonly used proxy for identification of marine environment entry during diadromous migrations. However, there is still controversy about the appearance of the Sr-based sea entry mark relative to the true point of entry. In this study, the Sr signal lag was assessed in otoliths of juvenile sockeye salmon (Oncorhynchus nerka) under experimental conditions replicating the transition to seawater during juveniles’ seaward migration. A Sr signal delay was observed to average at 8.2 (SD = 5.1) days for fish with a body length of 140–170 mm (and a weight of 30–70 g). This lag may be species-specific and should be taken into consideration when estimating marine entry timing and marine residence duration of juvenile salmon.

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