Microorganisms and higher plants produce biogenic ligands, such as siderophores, to mobilize Fe that otherwise would be unavailable. In this paper, we study the stability of arsenopyrite (FeAsS), one of the most important natural sources of arsenic on Earth, in the presence of desferrioxamine (DFO-B), a common siderophore ligand, at pH 5. Arsenopyrite specimens from mines in Panasqueira, Portugal (100-149 mu m) that contained incrustations of Pb, corresponding to elemental Pb as determined by scanning electron microscopy-electron diffraction spectroscopy (SEM-EDX), were used for this study. Batch dissolution experiments of arsenopyrite (1 g L-1) in the presence of 200 mu M DFO-B at initial pH (pH(0)) 5 were conducted for 110 h. In the presence of DFO-B, release of Fe, As, and Pb showed positive trends with time; less dependency was observed for the release of Fe, As, and Pb in the presence of only water under similar experimental conditions. Detected concentrations of soluble Fe, As, and Pb in suspensions containing only water were found to be ca. 0.09 +/- 0.004, 0.15 +/- 0.003, and 0.01 +/- 0.01 ppm, respectively. In contrast, concentrations of soluble Fe, As, and Pb in suspensions containing DFO-B were found to be 0.4 +/- 0.006, 0.27 +/- 0.009, and 0.14 +/- 0.005 ppm, respectively. Notably, the effectiveness of DFO-B for releasing Pb was ca. 10 times higher than that for releasing Fe. These results cannot be accounted for by thermodynamic considerations, namely, by size-to-charge ratio considerations of metal complexation by DFO-B. As determined by SEM-EDX, elemental sample enrichment analysis supports the idea that the Fe-S subunit bond energy is limiting for Fe release. Likely, the mechanism(s) of dissolution for Pb incrustations is independent and occurs concurrently to that for Fe and As. Our results show that dissolution of arsenopyrite leads to precipitation of elemental sulfur, and is consistent with a non-enzymatic mineral dissolution pathway. Finally, speciation analyses for As indicate variability in the As(III)/As(V) ratio with time, regardless of the presence of DFO-B or water. At reaction times < 30 h, As(V) concentrations were found to be 50-70 parts per thousand, regardless of the presence of DFO-B. These results are interpreted to indicate that transformations of As are not imposed by ligand-mediated mechanisms. Experiments were also conducted to study the dissolution behavior of galena (PbS) in the presence of 200 mu M at pH(0) 5. Results show that, unlike arsenopyrite, the dissolution behavior of galena shows coupled increases in pH with decreases in metal solubility at t > 80 h. Oxidative dissolution mechanisms conveying sulfur oxidation bring about the production of {H+}. However, dissolution data trends for arsenopyrite and galena indicate {H+} consumption. It is plausible that the formation of Pb species is dependent on {H+} and {OH-}, namely, stable surface hydroxyl complexes of the form Pb-4(OH)(4)(4+) (pH(50) 5.8) and Pbb(OH)(8)(4+) for pH values 5.8 or above. (c) 2008 Elsevier Ltd. All rights reserved.
