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The crystal structure of a naturally occurring layered double hydroxide mineral—desautelsite from San Benito County, California, USA—was refined using single-crystal X-ray diffraction data in the space group R-3m, a = 3.1238(2) Å, c = 23.528(3) Å, V = 198.83(4) ų, and Z = 3/8. The Mg and Mn cations are disordered occurring in one M site with occupancy Mg_0.77Mn_0.23. According to the electron microprobe analysis supported by Raman spectroscopy, the empirical formula is Mg_6.20(Mn^III_1.78Al_0.01Fe^III_0.01)_Σ1.80(OH)₁₆(CO₃)_0.90·5.35H₂O that shows higher content of interlayer (H₂O) molecules in comparison to the ideal formula that also agrees with the structure refinement. The Raman spectroscopy of two samples indicated O–H vibrations (3650/3640 cm⁻¹, ~3500 sh cm⁻¹), symmetric C–O (1055/1057 cm⁻¹), Mg–O–Mg (533/533 cm⁻¹) and Mn–O–Mn (439/438 cm⁻¹) stretching vibrations and lattice vibrations (284/287 cm⁻¹). Summing up our data and that of the current literature, we show a correlation (R² = 0.91) between the averaged effective ionic radius (x) and a unit cell parameter (y) of hydrotalcite group minerals, $y=1.9871x+1.4455$. Desautelsite follows this correlation, being the species with one of the largest a unit cell parameters among the group. The correlation can be applied for control of cation intercalation during synthesis. Full article

Manganese oxides are widespread in soils and natural waters, and their capacity to adsorb different trace metals such as Co, Ni, or Zn is well known. In this study, we aimed to compare the extent of trace metal coprecipitation in different Mn oxides formed during Mn(II) oxidation in highly concentrated, metal-rich mine waters. For this purpose, mine water samples collected from the deepest part of several acidic pit lakes in Spain (pH 2.7–4.2), with very high concentration of manganese (358–892 mg/L Mn) and trace metals (e.g., 795–10,394 µg/L Ni, 678–11,081 µg/L Co, 259–624 mg/L Zn), were neutralized to pH 8.0 in the laboratory and later used for Mn(II) oxidation experiments. These waters were subsequently allowed to oxidize at room temperature and pH = 8.5–9.0 over several weeks until Mn(II) was totally oxidized and a dense layer of manganese precipitates had been formed. These solids were characterized by different techniques for investigating the mineral phases formed and the amount of coprecipitated trace metals. All Mn oxides were fine-grained and poorly crystalline. Evidence from X-Ray Diffraction (XRD) and Scanning Electron Microscopy coupled to Energy Dispersive X-Ray Spectroscopy (SEM–EDX) suggests the formation of different manganese oxides with varying oxidation state ranging from Mn(III) (e.g., manganite) and Mn(III/IV) (e.g., birnessite, todorokite) to Mn(IV) (e.g., asbolane). Whole-precipitate analyses by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES), and/or Atomic Absorption Spectrometry (AAS), provided important concentrations of trace metals in birnessite (e.g., up to 1424 ppm Co, 814 ppm Ni, and 2713 ppm Zn), while Co and Ni concentrations at weight percent units were detected in asbolane by SEM-EDX. This trace metal retention capacity is lower than that observed in natural Mn oxides (e.g., birnessite) formed in the water column in a circum-neutral pit lake (pH 7.0–8.0), or in desautelsite obtained in previous neutralization experiments (pH 9.0–10.0). However, given the very high amount of Mn sorbent material formed in the solutions (2.8–4.6 g/L Mn oxide), the formation of these Mn(III/IV) oxides invariably led to the virtually total removal of Co, Ni, and Zn from the aqueous phase. We evaluate these data in the context of mine water pollution treatment and recovery of critical metals. Full article