Preservation procedures for arsenic speciation in a stream affected by acid mine drainage in southwestern Spain

A preservation study has been performed for arsenic speciation in surface freshwaters affected by acid mine drainage (AMD), a pollution source characterized by low pH and high metallic content. Two sample preservation procedures described in the literature were attempted using opaque glass containers and refrigeration: i) addition of 0.25 mol L−1 EDTA to the samples, which maintained the stability of the arsenic species for 3 h; and ii) in situ sample clean-up with a cationic exchange resin, in order to reduce the metallic load, which resulted in a partial co-adsorption of arsenic onto Fe precipitates. A new proposed method was also tried: sample acidification with 6 mol L−1 HCl followed by in situ clean-up with a cationic exchange resin, which allowed a longer preservation time of at least 48 h. The proposed method was successfully applied to water samples with high arsenic content, taken from the Aguas Agrias Stream (Odiel River Basin, SW Spain), which is severely affected by AMD that originates at the nearby polymetallic sulfide mine of Tharsis. The speciation results obtained by liquid chromatography–hydride generation–atomic fluorescence spectrometry (HPLC-HG-AFS) indicated that during the summer the main arsenic species was As(V) at the hundred μg L−1 level, followed by DMA (dimethyl arsenic) and As(III) below the ten μg L−1 level. In winter, As(V) and As(III) increased at least fivefold, whereas the DMA was not detected.