Determination of Fe(III) and Fe(II) in oxalate extracts of sediment

A method was developed to determine the concentrations of oxalate-extractable Fe(III) and Fe(II) in sediments. Sediment was extracted in acid ammonium oxalate under N₂. Iron(II) in the extract was determined with ferrozine. Iron(III) in the extract was reduced with hydroxylamine-hydrochloride, and total Fe in the extract was determined with ferrozine. Oxalate-extractable Fe(III) was calculated as the difference between Fe(II) and total Fe in the extract. Iron(II) was not oxidized, and Fe(III) was not reduced during the extraction. For an accurate estimate of oxalate-extractable Fe(III), fresh samples had to be analyzed, because air-drying or freeze-drying the samples oxidized Fe(II) to oxalate-extractable Fe(III). With a minimal increase in analytical effort, the method yields far more information on Fe geochemistry than the standard aerobic oxalate extraction method.