A method has been developed to analyse static 10B NMR spectra and, using exhaustive simulation procedures, we have obtained values for quadrupole parameters and their distribution. Experimental data for vitreous boron oxide, vitreous and crystalline caesium triborate, vitreous caesium diborate, crystalline potassium diborate, and caesium enneaborate have been fitted to yield information on the multiple sites and their quadrupole parameters. These sites may result from differences in short range order, or intermediate range structure. The asymmetry parameter is particularly sensitive to differences in the environments of three-coordinated borons placed in differing intermediate range order positions.