Respirable forms of crystalline silica including the mineral cristobalite are known carcinogens and the subject of increasing regulation and codes of good practice. Some bentonites may contain cristobalite, but more commonly they contain opal-CT, or opal-C, which can be confused with cristobalite. In the light of increasing regulation there is a clear need for simple and reliable methods that can distinguish cristobalite from the opals in bentonites and other clay materials. Here we propose the use of a simple NaOH method that is easily applied to bulk samples of bentonites. The method consists of boiling the clay in 0.5 m NaOH for 10 min and measuring the weight of undissolved solid. The method is shown to be accurate for both the identification and quantification of opal in bentonites since these phases are soluble when thus treated. It is also a straightforward method to distinguish the opals from cristobalite as the latter is essentially insoluble. Adoption by industry of a simple operationally-defined method such as this would be preferable to ad hoc reliance on direct instrumental methods alone such as X-ray powder diffraction, as the latter almost always require a large element of judgement and experience on the part of the analyst, although direct methods do need to be used in a supporting role.