Comparison of extraction procedures for arsenic speciation in environmental solid reference materials by high-performance liquid chromatography-hydride generation-atomic fluorescence spectroscopy

Water and ‘soft’ extractions (hydroxylammonium hydrochloride, ammonium oxalate and orthophosphoric acid) have been studied and applied to the determination of arsenic species (arsenite, arsenate, monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA)) in three environmental solid reference materials (river sediment, agricultural soil, sewage sludge) certified for their total arsenic content. The analytical method used was ion exchange liquid chromatography coupled on‐line to atomic fluorescence spectroscopy through hydride generation. Very low detection limits for arsenic were obtained, ranging from 0.02 to 0.04 mg kg−1 for all species in all matrices studied. Orthophosphoric acid is the best extractant for sediment (mixed origin) and sludge samples (recent origin) but not for the old formation soil sample, from which arsenic is extracted well only by oxalate. Both inorganic forms (As(III) and As(V)) are significant in all samples, As(V) species being predominant. Moreover, organic forms are found in water extracts of all samples and are more important in the sludge sample. These organic forms are also present in the ‘soft’ extracts of sludge. Microwave‐assisted extraction appears to minimize the risk of a redox interconversion of inorganic arsenic forms. This study points out the necessity of combining direct and sequential extraction procedures to allow for initial arsenic speciation and to elucidate the different mineralogical phases–species associations. Copyright © 2002 John Wiley & Sons, Ltd.