Laboratory exploration of mineral precipitates from Europa's subsurface ocean

The precipitation of hydrated phases from a chondrite-like Na–Mg–Ca–SO4–Cl solution is studied using in situ synchrotron X-ray powder diffraction, under rapid- (360 K h−1, T = 250–80 K, t = 3 h) and ultra-slow-freezing (0.3 K day−1, T = 273–245 K, t = 242 days) conditions. The precipitation sequence under slow cooling initially follows the predictions of equilibrium thermodynamics models. However, after ∼50 days at 245 K, the formation of the highly hydrated sulfate phase Na2Mg(SO4)2·16H2O, a relatively recent discovery in the Na2Mg(SO4)2–H2O system, was observed. Rapid freezing, on the other hand, produced an assemblage of multiple phases which formed within a very short timescale (≤4 min, ΔT = 2 K) and, although remaining present throughout, varied in their relative proportions with decreasing temperature. Mirabilite and meridianiite were the major phases, with pentahydrite, epsomite, hydrohalite, gypsum, blödite, konyaite and loweite also observed. Na2Mg(SO4)2·16H2O was again found to be present and increased in proportion relative to other phases as the temperature decreased. The results are discussed in relation to possible implications for life on Europa and application to other icy ocean worlds.

Thermodynamic Analysis of Precipitation Characteristics of Rare Earth Elements with Sulfate in Comparison with Other Common Precipitants

The selective precipitation of rare earth elements (REEs) in acidic media often plays a key role in the effective extraction of these elements from various sources such as ores and recycling streams. In this study, the precipitation characteristics of REEs with sulfate, a frequently used precipitant, were carefully examined, and the results were compared with those of other precipitants, such as phosphate, oxalate, and fluoride/carbonate systems. Emphasis is given on various forms of precipitates, such as anhydrous sulfate, octa-hydrated sulfate, and sodium double salt, in which the sodium double salt was compared with the anionic double salt precipitation of the fluoride-carbonate system. It was found that anions such as Cl−, NO3−, and SO42− play an important role in the precipitation behavior, particularly through complexation with the dissolved REEs. In general, the effectiveness of precipitation follows the order of sodium double salt, a hydrated form of sulfate, and anhydrous sulfate. In this study, it was observed that the synergistic role of a double salt precipitation, either cationic or anionic, is frequently as effective as that of oxalate and phosphate, even in a low pH range.

Tripodal, Squaramide-Based Ion Pair Receptor for Effective Extraction of Sulfate Salt

Combining three features—the high affinity of squaramides toward anions, cooperation in ion pair binding and preorganization of the binding domains in the tripodal platform—led to the effective receptor 2. The lack of at least one of these key elements in the structures of reference receptors 3 and 4 caused a lower affinity towards ion pairs. Receptor 2 was found to form an intramolecular network in wet chloroform, which changed into inorganic–organic associates after contact with ions and allowed salts to be extracted from an aqueous to an organic phase. The disparity in the binding mode of 2 with sulfates and with other monovalent anions led to the selective extraction of extremely hydrated sulfate anions in the presence of more lipophilic salts, thus overcoming the Hofmeister series.

Redefinition of coquimbite, AlFe3+3(SO4)6(H2O)12⋅6H2O

Coquimbite, AlFe3+3(SO4)6(H2O)12⋅6H2O, was considered as a pure Fe3+ hydrated sulfate. However, previous mineralogical studies pointed out the occurrence of essential Al, occupying a distinct site in the crystal structure of this mineral. Through the critical re-examination of the available literature and new crystal-chemical data collected on a specimen from the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy, the chemical formula of coquimbite has been revised, taking into account the occurrence of Al. Coquimbite has a homeotypic relationship with paracoquimbite, Fe4(SO4)6(H2O)12⋅6H2O; both mineral species belong to the coquimbite group. On the contrary, aluminocoquimbite, Al2Fe2(SO4)6(H2O)12⋅6H2O, has a different topology and does not belong to that group.