Rock, soil, or sediment samples are decomposed with a mixture of nitric and sulphuric adds. After reduction from arsenic(V) with ammonium thiosulphate, arsenic(III) is extracted as the chlorocomplex into benzene from a sulphuric-hydrochloric acid medium. The benzene solution is transferred onto a filter-paper disc impregnated with a solution of sodium bicarbonate and potassium sodium tartrate, and the benzene allowed to evaporate. The arsenic present is determined by X-ray fluorescence. In a 0.5-g sample, 1-1000 ppm of arsenic can be determined. The close proximity of the lead L?? peak (2?? 48.73??), to the arsenic K?? peak (2?? 48.83??) does not cause any interference, because lead is not extracted under the experimental conditions. Arsenic values obtained are in agreement with those reported for various reference samples. ?? 1983.