This paper reviews the current knowledge on the toxicity, speciation and biogeochemistry of arsenic in aquatic environmental systems. The toxicity of arsenic is highly dependent on the chemical speciation. The effects of pH, E(h), adsorbing surfaces, biological mediation, organic matter, and key inorganic substances such as sulfide and phosphate combine in a complex and interwoven dynamic fashion to produce unique assemblages of arsenic species. The number of different arsenic species found in environmental samples and an understanding of the transformations between arsenic species has increased over the past few decades as a result of new and refined analytical methods. Changes in arsenic speciation and in total arsenic content of foods upon processing have suggested possible risks associated with processed and unprocessed food. Arsenic removal from water using adsorbents, chemical oxidation, photolysis and photocatalytic oxidation techniques is also reviewed.