文摘
Short-range ordered ferric arsenate (FeAsO4路xH2O) is a secondary As precipitate frequently encountered in acid mine waste environments. Two distinct structural models have recently been proposed for this phase. The first model is based on the structure of scorodite (FeAsO4路2H2O) where isolated FeO6 octahedra share corners with four adjacent arsenate (AsO4) tetrahedra in a three-dimensional framework (framework model). The second model consists of single chains of corner-sharing FeO6 octahedra being bridged by AsO4 bound in a monodentate binuclear 2C complex (chain model). In order to rigorously test the accuracy of both structural models, we synthesized ferric arsenates and analyzed their local (<6 脜) structure by As and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. We found that both As and Fe K-edge EXAFS spectra were most compatible with isolated FeO6 octahedra being bridged by AsO4 tetrahedra (RFe鈥揂s = 3.33 卤 0.01 脜). Our shell-fit results further indicated a lack of evidence for single corner-sharing FeO6 linkages in ferric arsenate. Wavelet-transform analyses of the Fe K-edge EXAFS spectra of ferric arsenates complemented by shell fitting confirmed Fe atoms at an average distance of 5.3 脜, consistent with crystallographic data of scorodite and in disagreement with the chain model. A scorodite-type local structure of short-range ordered ferric arsenates provides a plausible explanation for their rapid transformation into scorodite in acid mining environments.