The Danxia landform is representative of the Cretaceous continental red sediment. The careful identification and potential environmental effects of minerals in Danxia red beds have yet to be clearly reported. In this work, reddish sandstone samples were collected from Lang Mountain Danxia landform in Xinning, Hunan province, China, and their mineral phases, element distribution, microstructure, and the spatial relationship of different minerals were investigated using polarizing optical microscope, environmental scanning electron microscopy, energy-dispersive X-ray analysis, electron probe microanalysis, micro-Raman spectra, micro- X-ray diffraction, X-ray fluorescence spectroscopy, and high-resolution transmission electron microscopy. The results revealed that iron oxide (mainly hematite) and titanium oxide (mainly anatase) were the dominant minerals in Danxia red layers. Microcrystalline hematite was suggested as being the coloring mineral. Anatase, reported here for the first time in Danxia red beds, constituted the content of titanium in the red layer (0.17–0.57%) and was present in a significantly higher amount than the adjacent limestone formation (0.13%). Over 95% of Fe/Ti oxides served as a cementation agent along the framework of coarse-grain minerals (quartz and feldspar). The hematite and anatase were visible-light-responsive semiconductors, with a band gap of 2.01 eV and 3.05 eV, respectively. Photoelectrochemical experiments were performed on synthetic hematite, anatase, and their coupled material. The inactive hematite displayed an enhanced 23-fold photocurrent at 0.8 V (vs. Ag/AgCl) when coupled with anatase. Furthermore, in a photodegradation experiment using methyl orange dye under simulated sunlight, the coupled material showed decolorizing efficiency 2.4 times that of hematite. The anatase, therefore, prominently improved the photocatalytic activities of hematite. It is proposed that these semiconducting minerals in red beds produce oxygen reactive species and have significant environmental effects, which is of great importance.

The complex environmental conditions at Cr-contaminated sites, characterized by uneven ion distribution, oxidants competition, and limited solid-phase mobility, lead to inadequate mixing of Fe-based reducing agents with Cr, posing significant challenges to the effectiveness of Cr remediation through Cr-spinel precipitation. This study investigates the distinct roles of Fe(II), Fe(III), and Cr(III) in Cr-spinel crystallization under ambient temperature and pressure. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray absorption near-edge structure spectroscopy, and Mössbauer spectroscopy were employed to elucidate the phase composition, microstructure, and ion coordination within the precipitates. Our findings indicate that Fe(II) acts as a catalyst in the formation of the spinel phase, occupying octahedral sites within the spinel structure. Under the catalytic influence of Fe(II), Fe(III) transitions into the spinel phase, occupying both the tetrahedral and the remaining octahedral sites. Meanwhile, Cr(III), due to its high octahedral site preference energy, preferentially occupies the octahedral sites. When Fe(II) or Fe(III) is present but does not meet the ideal stoichiometric ratio, a deficiency in Fe(II) leads to low yield and poor crystallinity of Cr-spinel, whereas a deficiency in Fe(III) can completely inhibit its formation. Conversely, when either Fe(II) or Fe(III) is in excess, the formation of Cr-spinel remains feasible. Furthermore, metastable Cr phases can be transformed into stable Cr-spinel by adjusting the Fe(II)/Fe(III)/Cr(III) ratio. These results highlight the broad range of conditions under which Cr-spinel mineralization can occur in environmental settings, enhancing our understanding of the mechanisms driving Cr-spinel formation in Cr-contaminated sites treated with Fe-based reducing agents. This research provides critical insights for optimizing Cr remediation strategies.