The two-step neutralization ferrite-formation process for sustainable acid mine drainage treatment: Removal of copper, zinc and arsenic, and the influence of coexisting ions on ferritization.

Acid mine drainage (AMD) or acid rock drainage (ARD), the most notorious environmental problem in many mines and underground construction sites, is generally managed using lime neutralization. This approach is effective but unsustainable in the long term, so we introduced the two-step neutralization ferrite-formation process in our previous works as an alternative. However, several important issues related to this new approach-the partitioning of hazardous elements during treatment, stability of generated sludges, and influence of coexisting ions-remains unclear. In this study, real AMD containing zinc (Zn), copper (Cu) and arsenic (As) was treated using a laboratory-type continuous ferrite process flow setup. Partitioning of hazardous elements in the two sludges was elucidated by X-ray fluorescence spectroscopy (XRF) and X-ray absorption spectroscopy (XAS) while the stability of sludges was determined by standard leaching experiments. The bulk of Cu and As species (both As(III) and As(V) based on XANES spectra) were partitioned in the first sludge while ~64% of Zn was associated with the ferrite sludge. In terms of stability, both sludges were relatively inert and released only minute amounts of Zn, Cu and As, all of which were below the Japanese environmental standards. The roles played by two of the most ubiquitous coexisting ions in AMD on ferritization-dissolved silica (Si) and aluminum ion (Al3+)-were also elucidated using 10 synthetic AMDs. Between the two, dissolved Si exhibited stronger adverse effects on ferritization than Al3+. At dissolved Si above 4 mg/L, Si-O-Fe surface complex formation on amorphous Fe-precipitates or Fe-oxide precursor minerals became extensive, which protected these phases from the dissolution-transformation reactions required to form strongly magnetic magnesioferrite and magnetite. These results suggest that the flexibility and applicability of this new AMD treatment approach could be improved by controlling the dissolved Si concentration prior to the ferrite formation step.

Simultaneous leaching of arsenite, arsenate, selenite and selenate, and their migration in tunnel-excavated sedimentary rocks: I. Column experiments under intermittent and unsaturated flow.

Rocks excavated in tunnel construction projects for roads and railways throughout Japan often leached out hazardous trace elements like arsenic (As) and selenium (Se) upon their exposure to the environment. In nature, the various oxyanionic species of As and Se not only coexist but also exhibit contrasting adsorption-desorption behaviors, so speciation is a crucial factor in their migration through natural geologic media. In this study, the leaching and transport of arsenite (AsIII), arsenate (AsV), selenite (SeIV) and selenate (SeVI) in four tunnel-excavated rocks from the Cretaceous-Paleocene Yezo forearc basin were investigated using laboratory column experiments supplemented by batch leaching experiments. The single- and consecutive-batch leaching results revealed that AsIII, AsV, SeIV and SeVI were released simultaneously, which could be attributed to the rapid dissolution of trace evaporite salts found in the rocks. Arsenic in the leachates was also predominated by AsV while SeIV and SeVI concentrations were nearly equal, which are both consistent with predictions of equilibrium Eh-pH diagrams. Under intermittent and unsaturated flow, however, periods when AsIII and SeVI predominated in the effluents were observed. Spatial distributions of As and Se species with depth at the end of the column experiments suggest that migrations of AsIII, AsV and SeIV were delayed, the extent of which depended on the rock. These results indicate that migration and speciation of As and Se in the rocks are controlled by preferential adsorption-desorption reactions, the effects of which were most probably magnified by changes in the pH and concentrations of coexisting ions due to intermittent and unsaturated flow.

Short and long term release mechanisms of arsenic, selenium and boron from a tunnel-excavated sedimentary rock under in situ conditions.

Sedimentary rocks of marine origin excavated from tunnel construction projects usually contain background levels of hazardous trace elements, but when exposed to the environment, they generate leachates with concentrations of arsenic (As), selenium (Se) and boron (B) exceeding the WHO guideline for drinking water. In this study, the leaching of As, Se and B was evaluated under in situ conditions at various flow patterns, particle size distributions and column thicknesses. The results showed that these trace elements were leached out of the rock via short and long term mechanisms. In the short term, all three elements were rapidly and simultaneously released due to the dissolution of soluble evaporite salts formed from entrapped sea water of the Cretaceous. After their rapid release, however, these trace elements behaved differently as a result of their contrasting adsorption affinities onto minerals like clays and Fe-oxyhydroxides, which were further influenced by the pH, presence of coexisting ions and speciation of the trace elements. Selenium was quickly and easily transported out of the columns because it was mostly present as the very mobile selenate ion (Se[VI]). In comparison, the migration of As and B was hindered by adsorption reactions onto mineral phases of the rock. Boron was initially the least mobile among the three because of its preferential adsorption onto clay minerals that was further enhanced by the slightly alkaline pH and high concentrations of Ca(2+) and Na(+). However, it was gradually re-mobilized in the latter part of the experiments because it was only weakly adsorbed via outer sphere complexation reactions. In the long term, the rock continued to release substantial amounts of As, Se and B via pyrite oxidation and adsorption/desorption reactions, which were regulated by the temperature and rainfall intensity/frequency on site.

Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release.

Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite.

Leaching of boron, arsenic and selenium from sedimentary rocks: I. Effects of contact time, mixing speed and liquid-to-solid ratio.

Sedimentary rocks of marine origin excavated in tunnel projects were recently identified as potentially hazardous because they could release significant amounts of toxic trace elements when exposed to the environment. This study investigated the leaching characteristics of B, As, Se and the major coexisting ions under various conditions to identify the factors and processes controlling their evolution in the leachate. In addition, we evaluated whether the parameters of the currently used leachability test for excavated rocks were adequate. Although the leachabilities of B, As and Se similarly increased at longer contact times, only those of B and As were influenced by the mixing speed and/or liquid-to-solid ratio (L/S). The majority of trace elements dissolved in the leachate originated from the dissolution of soluble salts formed from seawater of the Cretaceous trapped during the formation of the sedimentary rocks. Moreover, the alkaline pH of the leachates could be attributed to the simultaneous dissolutions at varying degrees of the mineral components of the rocks as well as the precipitation of clay minerals. In the leaching test of excavated rocks for regulatory purposes, the best values of contact time and mixing speed should represent conditions of the highest trace element extractabilities, which in this study were found at longer contact times (>48 h) and the fastest mixing speed (200 rpm). The most appropriate L/S for the leaching test is 10 because it was around this L/S that the extractabilities and leaching concentrations of the trace elements were simultaneously observed at their highest values.