Different extraction procedures were applied to improve the extraction efficiency of arsenic compounds from lichens. Two lichen species were chosen from an arsenic-contaminated environment: epiphytic Hypogymnia physodes (L.) Nyl. and terricolous Cladonia rei Schaer. Samples were extracted with water at temperatures of 20, 60 and 90 degrees C, using mixtures of methanol/water (9:1, 1:1 and 1:9), Tris buffer and acetone and the extracts speciated. Water and Tris buffer showed the best extraction efficiency of all extractants used; however, the extraction efficiency was still less than 23%. Since a major fraction of arsenic appeared to be associated with trapped soil particles, a sequential extraction procedure originally designed for soils (extraction steps: (1) 0.05 mol l(-1) (NH(4))(2)SO(4); (2) 0.05 mol l(-1) (NH)(4)H(2)PO(4); (3) 0.2 mol l(-1) NH(4)-oxalate buffer, pH 3.25; (4) mixture of 0.2 mol l(-1) NH(4)-oxalate buffer and 0.1 mol l(-1) ascorbic acid, pH 3.25; (5) 0.5 mol l(-1) KOH) was applied and found to remove 45% of the total arsenic from H. physodes and 83% from C. rei. The lipid-soluble fraction of arsenic was estimated by k(0)-INAA analysis of diethylether extracts and was found to be negligible. An HPLC-UV-HGAFS system was used to determine the arsenic compounds extracted. In both lichen species, arsenous acid, arsenic acid, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, trimethylarsine oxide and glycerol-ribose were detected. In addition, phosphate-ribose was found in H. physodes.