Natural attenuation of arsenic in the environment by immobilization in nanostructured hematite. (November 2015) - Freitas, Erico T.F.
Graphical abstract: Highlights: Identification of As-bearing Al-hematite in environmental samples. A mechanism of As fixation into Al-hematite mesocrystals by oriented attachment. Microscopy techniques analyses of trace element distribution in environmental samples. Significance of these findings for the management of As-contaminated mine sites. Abstract: Iron (hydr)oxides are known to play a major role in arsenic fixation in the environment. The mechanisms for long-term fixation into their crystal structure, however, remain poorly understood, especially arsenic partitioning behavior during transformation from amorphous to crystalline phases under natural conditions. In this study, these mechanisms are investigated in Fe–Al-oxisols exposed over a period of 10 years to a sulfide concentrate in tailings impoundments. The spatial resolution necessary to investigate the markedly heterogeneous nanoscale phases found in the oxisols was achieved by combining three different, high resolution electron microscopy techniques – Nano-Beam Electron Diffraction (NBD), Electron Energy-Loss Spectroscopy (EELS), and High Resolution Transmission Electron Microscopy (HRTEM). Arsenic (1.6 ± 0.5 wt.%) was unambiguously and precisely identified in mesocrystals of Al-hematite with an As/Fe atomic ratio of 0.026 ± 0.006. The increase in the c -axis ( c = 1.379 ± 0.009 nm) compared to standard hematite ( c = 1.372 nm) is consistent with the presence of arsenic in the Al-hematite structure. The As-bearing Al-hematite is interpreted as a secondary phase formed from oxyhydroxides, such as ferrihydrite, during the long-term exposure to the sulfide tailings. The proposed mechanism of arsenic fixation in the Al-hematite structure involves adsorption onto Al-ferrihydrite nanoparticles, followed by Al-ferrihydrite aggregation by self-assembly oriented attachment and coalescence that ultimately produces Al-hematite mesocrystals. Our results illustrate for the first time the process of formation of stable arsenic bearing Al-hematite for the long-term immobilization of arsenic in environmental samples.