Stripping voltammetry capable of detecting 0.3microg/L arsenate and arsenite was applied for speciation analysis of arsenic sorbed onto synthetic ferrihydrite, goethite at As/Fe ratio of approximately 1.5mg/g with or without birnessite after sequential extraction using 1M phosphate (24 and 16 h) and 1.2M HCl (1h). Precautions to avoid oxygen were undertaken by extracting under anaerobic conditions and by adding 0.1M l-ascorbic acid to 1M NaH(2)PO(4) (pH 5). Addition of l-ascorbic acid did not reduce As(V) to As(III). The recovery rate for As(III) using l-ascorbic acid for extraction (pH 5) but not for adsorption was 81% and 74% of total sorbed As, and was 99% and 97% of extracted As for ferrihydrite and goethite, respectively. Birnessite oxidized most As(III) during the adsorption procedure. l-ascorbic acid used both in adsorption and extraction procedures improved the recovery of As(III) to 79-94% for ferrihydrite-birnessite and 57-94% for goethite-birnessite systems with Fe/Mn ratios of 7, 70, 140 and 280g/g.