NMR spectroscopy has recently emerged as a powerful method for studying electrolyte species in microporous carbon electrodes used in capacitive energy storage devices. Key to this approach is the nucleus-independent chemical shift (NICS) which enables adsorbed species to be distinguished from those in the bulk electrolyte. The magnitude of the NICS is well known to be dependent on the distance of the adsorbed species from the carbon surface, and has therefore been used in several studies as a probe of the carbon pore size. However, the NICS can also be influenced by a number of other structural and chemical factors which are not always taken into account. To investigate this, we have carried out a systematic study of the factors influencing the NICS of aqueous electrolyte species adsorbed on polymer-derived activated carbon in the absence of an applied potential. We find that a number of effects arising from both the carbon structure as well as the behaviour and chemical properties of the electrolyte species can contribute to the observed NICS. In turn, the measurement of these effects provides important information about ion behaviour and reveals significant differences in the adsorption behaviour of different ions in the absence of an applied potential. In accordance with several computational studies, we find experimental evidence that the local concentration of spontaneously adsorbed alkali ions decreases with the pore size. This has potential implications for understanding the molecular-level mechanism of charge storage in capacitive devices.