Calculating % natural abundance of isotopes from % relative abundance in a mass spectrum

A mass spectrum is a plot of the % relative abundance of cations that have arisen from ionisation of the sample against their mass to charge ratio (m/z).

The ionisation is the result of an electron being stripped from the atoms (molecules) present in a sample that is analysed used an instrument called a mass spectrometer.  Because the charge (z) on the cations produced in the mass spectrometer is nearly always +1, the ratio m/z is equal to the mass number of the atom(s) in the cation.
 
The cation in largest abundance is assigned a % relative abundance of 100%.

The abundances of others are relative to this one. 
 
mass spec Si

In the mass spectrum of elemental silicon that is shown,
28Si has a % relative abundance of 100.0%, with 29Si being 5.1% and 30Si being 3.4%.
The sum of the % relative abundnaces is greater than 100% (108.5% in this case)
 
The sum of the % natural abundances of the isotopes is equal 100%.
 
For example the % natural abundance for  chlorine is 75% 37Cl and 25% 35Cl.
Compare this with the relative abundances from the mass spectrum which would be 100% 37Cl and 33% 35Cl.  Note that the relative abundances are larger than the % natural abundance.

The % natural abundance of any isotope can be calculated from the % relative abundances.
 
% natural abundance
28Si
= % relative abundance 28Si × 100%
sum % relative abundance of all isotopes
 
% natural abundance
28Si
= 100 × 100%= 92%
100+5.1+3.4

Thus the % natural abundance of any isotope is lower than its % relative abundance in the mass spectrum.