Sugarcane leaves contain amorphous silica, which may crystallise to form crystalline silica polymorphs (cristobalite or quartz), during commercial sugarcane harvesting where sugarcane plants are burned. Respirable airborne particulate containing these phases may present an occupational health hazard. Following from an earlier pilot study (J. S. Le Blond, B. J. Williamson, C. J. Horwell, A. K. Monro, C. A. Kirk and C. Oppenheimer, Atmos. Environ., 2008, 42, 5558-5565) in which experimental burning of sugarcane leaves yielded crystalline silica, here we report on actual conditions during sugarcane burning on commercial estates, investigate the physico-chemical properties of the cultivated leaves and ash products, and quantify the presence of crystalline silica. Commercially grown raw sugarcane leaf was found to contain up to 1.8 wt\% silica, mostly in the form of amorphous silica bodies (with trace impurities e. g., Al, Na, Mg), with only a small amount of quartz. Thermal images taken during several pre-harvest burns recorded temperatures up to 1056 degrees C, which is sufficient for metastable cristobalite formation. No crystalline silica was detected in airborne particulate from pre-harvest burning, collected using a cascade impactor. The sugarcane trash ash formed after pre-harvest burning contained between 10 and 25 wt\% SiO2, mostly in an amorphous form, but with up to 3.5 wt\% quartz. Both quartz and cristobalite were identified in the sugarcane bagasse ash (5-15 wt\% and 1-3 wt\%, respectively) formed in the processing factory. Electron microprobe analysis showed trace impurities of Mg, Al and Fe in the silica particles in the ash. The absence of crystalline silica in the airborne emissions and lack of cristobalite in trash ash suggest that high temperatures during pre-harvest burning were not sustained long enough for cristobalite to form, which is supported by the presence of low temperature sylvite and calcite in the residual ash. The occurrence of quartz and cristobalite in bagasse ash is significant as the ash is recycled onto the fields where erosion and/or mechanical disturbance could break down the deposits and re-suspend respirable-sized particulate. Appropriate methods for treatment and disposal of bagasse ash must, therefore, be employed and adequate protection given to workers exposed to these dusts.