Understanding the form of Se(IV) co-precipitated with ferrihydrite and its subsequent behavior during phase transformation is critical to predicting its long-term fate in a range of natural and engineered settings. In this work, Se(IV)-ferrihydrite co-precipitates formed at different pH were characterized with chemical extraction, transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS) to determine how Se(IV) is associated with ferrihydrite. Results show that despite efficient removal, the mode and stability of Se(IV) retention in the co-precipitates varied with pH. At pH 5, Se(IV) was removed dominantly as a ferric selenite-like phase intimately associated with ferrihydrite, while at pH 10, it was mostly present as a surface species on ferrihydrite. Similarly, the behavior of Se(IV) and the extent of its retention during phase transformation varied with pH. At pH 5, Se(IV) remained completely associated with the solid phase despite the phase change, whereas it was partially released back into solution at pH 10. Regardless of this difference in behavior, TEM and XAS results show that Se(IV) was retained within the crystalline post-aging products and possibly occluded in nanopore and defect structures. These results demonstrate a potential long-term immobilization pathway for Se(IV) even after phase transformation. This work presents one of the first direct insights on Se(IV) co-precipitation and its behavior in response to iron phase transformations.

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The SW sector of Mount Natib, a potentially active volcano in the Bataan volcanic arc in western Luzon, is the site of a mothballed nuclear power plant that members of the national legislature have proposed to activate. Detailed geological fieldwork was conducted to assess the capability of the volcano and to identify any volcanic hazards it might pose to the nuclear plant. The nearest eruptive centre is 5.5 km away from the plant. SW Natib Volcano is underlain by lava flows, lahar deposits and at least six pyroclastic density current (PDC) deposits, three directly underlying the nuclear reactor facility. A fault trending N308E is aligned with the Lubao Fault, a capable fault NE of the volcanic edifice. Radon emissions at the traces of these faults are high and comparable to those at known active faults. An associated thrust fault at the nuclear site cuts through lahars up to the ground surface. The results presented here can be used for general hazard preparedness of local communities, and may assist the government to decide whether or not to recommission the nuclear power plant.

Immobilization of Se(IV) by adsorption on iron oxides exerts a key control on its mobility in a number of natural and engineered settings; however, the presence of other coexisting ligands may influence the extent and stability of adsorption. In this work, we investigated the impacts of Si, which is an abundant component of many natural waters, on Se(IV) adsorption and retention on ferrihydrite. Using in situ ATR-IR spectroscopy, we obtained time-resolved information on Se(IV) adsorption on ferrihydrite in the presence of Si at pH 5, 7, and 9. The results show that Si inhibited the adsorption of Se(IV) at all pH if Si was initially adsorbed on ferrihydrite. This was attributed to the oligomerization of Si on ferrihydrite, which blocked Se(IV) from binding to ferrihydrite. In experiments where Se(IV) was initially adsorbed, Si was found to induce Se(IV) desorption. Competitive adsorption experiments, where Se(IV) and Si were present in the same solution, showed that Si negligibly affected Se(IV) adsorption at pH 5 and 7, likely because of lower Si adsorption and the lack of considerable oligomerization. On the other hand, at pH 9, Se(IV) was initially adsorbed and then subsequently desorbed with increasing Si adsorption and oligomerization. Hence, Si affects Se(IV) adsorption over a narrower pH range than when it is preadsorbed on ferrihydrite. These results show that Si can enhance Se(IV) mobility and highlight the influence of pH and the timing of Si adsorption in inhibiting Se(IV) adsorption on ferrihydrite. This work offers the first direct insights into the dynamic processes underpinning Se(IV) and Si competitive adsorption, which may be useful in understanding Se(IV) behavior in a broad range of environmental settings.