Synthesis of Scorodite Coated in-Situ with Hydrated Ferric Oxide and its Leaching Stability

"To overcome the problem that scoroditeis not stable in neutral and alkaline solutions, we proposed and investigated a synthesis method of scorodite coated in-situ with hydrated ferric oxide in the Fe(II)-As(V)-H2O system at the initial Fe(III)/As(V) molar ratios larger than 1.0.The synthesis was carried out at 90?,pH 1.5 under atmospheric pressure. During the synthesis, oxygen gas was conducted and bubbled into the system to oxidize Fe(II) ions into Fe(III)ions, and Na2CO3aqueous solution as neutralizing agent was added controllably into the system for keeping the pH constant at 1.5. In this study, three samples of scorodite were synthesized at the controlled initial Fe(II)/As(V) molar ratios of 1.0, 2.0 and 3.0, respectively. The characterizations of the samples by HRTEM, TEM/EDX, and chemical composition indicated that the particle surfaces of scorodite synthesized at the initial Fe(II)/As(V) molar ratio of 2.0 and 3.0 were coated in situ by a film of hydrated ferric oxide with the thickness of several nanometers, while the sample synthesized at the initial Fe(II)/As(V) molar ratio of 1.0 was uncoated scorodite. The TCLP and long-term leaching for the toxicity characteristic of the samples showed that scorodite coated in situ with hydrated ferric oxide was stable in a wide pH range from 3.0 to 10.0, with the arsenic concentrations in the leaching solutions less than 1.0mg/L. Nevertheless, uncoated scorodite was unstable under the conditions from weak acidity to alkalinity, with the arsenic concentrations in the leaching solutions larger than 5.0 mg/L.INTRODUCTIONArsenic pollution is a challenge for environment and health and has been an important issue for scientists (Hopkin, 1989).Arsenicis commonly associated with ores or concentrates of nonferrous metals, mainly as independent arsenic bearing minerals such as arsenopyrite (FeAsS), tennantite(Cu12As4S13), enargite (Cu3AsS4), cobaltite (CoAsS), and gersdorffite (NiAsS), realgar (As2S2), orpiment(As2S3), etc.(Matschullat, 2000; Mandal & Suzuki, 2002; Long & Peng, 2012). In the nonferrous metallurgical processes, arsenic is enriched mainly in such arsenic bearing materials as various flue dusts, residues, and anode slimes, which results in the accumulation of arsenic in the system owing to the circulation of those arsenic-bearing materials back to the system and the pollution to the environment (Harris, et al, 2003).In addition, the utilization of arsenic is limited and has been decreasing owing to its toxicity and carcinogenicity. Therefore, arsenic has to be removed from those arsenic-bearing materials and discarded safely (Dutrizac & Jambor, 1988; Monhemius & Swash, 1999; Drahota & Fillippi, 2009).In this case, how to immobilize arsenic has become a difficult problem which must be solved. Among the methods of immobilizing arsenic which have been proposed and investigated, immobilizing arsenic into a stable mineral to fix it, has been realized as a promising method and becomes a research focus(Dutrizac et al, 1987; Dutrizac & Jambor, 1988; Demopoulos et al, 1995; Fujita et al, 2008a; 2008b).Scorodite has been known as one of the best minerals for immobilizing arsenic, owing to its high stability under weak acidic condition, the arsenic content as high as 32wt%,and good crystallinity benefiting the separation of solid to liquid(Daivid et al, 1999; Zhu & Merkel, 2001). Scorodite can be synthesized from arsenic containing solutions under both hydrothermal and atmospheric conditions, and a lot of work has been done on the synthesis of scorodite and its leaching stability characterization (Filippou & Demopoulos, 1999; Gomez et al, 2011).Two plants for the immobilization of arsenic as scorodite have been putin to operation in Chile and Japan, respectively (Filippou & Demopoulos, 1999; Amir et al, 2016)."