Molybdenum linearity issues using 7800 ICP-MS

Using ICP-MS 7800 with Helium mode for Mo assessment, as you can see from attached picture we are having some issues. Calibrating range goes from 0.1ppb (actually excluded so 1 ppb as the lower point but this changes nothing) up to 1000ppb, the higher standard seems to be overextimated (if you exclude it you would see its dot clearly above the new calibration line, also looking at CPS they seem ~10% higher than expected according to the lower points).
Also with that calibration the other standards calculated value is ~ 10% lower than the nominal value for the "closer" one and ~ 20% lower for the 1 & 10ppb std wich also points to a linearity problem.
This has been a constant issue in the last months so it's not a random effect that may be related to standard preparation.

I've noticed that the higher calibration point is determined in analog mode while the others are all in pulse mode, could there be a problem with P/A Factor? We run a separated P/A setting using Agilent PA tuning solutions 1+2 diluted 1:100 before calibration (with the "merge" option checked) and also use the p/a adjustment setting into acquisition so it should work properly. 

According to the latest tune report detector voltages seems good so shouldn't be a detector problem.

Any insight? Is there something I could try (besides narrowing the calibration range wich I don't want to do)?  

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  • Have you tried enabling the "independent P/A factor" in settings?  Using this along with the P/A factor adjustment in the batch will allow for P/A factors to be collected for all tune modes.  Note that the independent P/A factor column header is added to the Acquisition Parameters section of the batch and also needs to be enabled in the batch.  I know this may be a long shot since you are not having issues with Ni which is in the same tune mode but perhaps the sensitivities are different enough.  Also, have you tried running Mo in a batch with only a single tune mode?

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  • Have you tried enabling the "independent P/A factor" in settings?  Using this along with the P/A factor adjustment in the batch will allow for P/A factors to be collected for all tune modes.  Note that the independent P/A factor column header is added to the Acquisition Parameters section of the batch and also needs to be enabled in the batch.  I know this may be a long shot since you are not having issues with Ni which is in the same tune mode but perhaps the sensitivities are different enough.  Also, have you tried running Mo in a batch with only a single tune mode?

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