Short-wave infrared (SWIR) spectral reflectance of the hydrothermally altered volcanic rocks in the footwall of the Hellyer Zn-Pb massive sulfide deposit was measured with a portable PIMATM infrared spectrometer. The Al-OH absorption band was used to derive information on the cation composition of white mica. The wavelength range of the Al-OH band from 2194 nm to 2222 nm reflects variation in the number of octahedral Al (Alvi) in white mica from 3.9 to 3.2 (based on four octahedral cations per formula). This Alvi range indicates a substantial compositional variation, covering most of the compositional region between muscovite (Alvi = 4.0) and phengite (Alvi = 3.0). Moreover, the spectral reflectance data show that the compositional variations of white mica are spatially related to the hydrothermal alteration zoning, such that the white mica of more phengitic composition tends to form in the main upflow fluid channels in the centre of the footwall alteration system. The results suggest that the octahedral Al content of white mica, which is spectrally definable by the wavelength of the Al-OH band using a field instrument such as the PIMATM, can be used to map fossil hydrothermal systems and potentially as vectors to mineralisation.