Dear Neil,

Sorry this may be too exact an interpretation of your English, but if you are 
looking at the exafs  then calibration is normally pretty irrelevant as long as 
it is not wildly out, as you refine E0 anyway in the fitting.
The bond distances will be very little altered by this.

If you are looking at XANES and it is 3/4  then CeL3  as I am sure you know has 
two "white lines" for four and one for three and the ratio of the two peaks can 
be used to
Look at oxidation state mixtures, I think  you should be able to align the 
peaks and fit the area e.g. Burnham AD, Berry AJ, 2014, The effect of oxygen 
fugacity, melt composition, temperature and pressure on the oxidation state of 
cerium in silicate melts, Chemical Geology, Vol:366, ISSN:0009-2541, Pages:52-60

Best wishes
Fred





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