^1,2Shuya Tan et al. (>10)
Geochimica et Cosmochimica Acta (in Press) Open Access Link to Article [DOI: 10.1016/j.gca.2026.06.034]
¹Earth and Space Exploration Center, Ritsumeikan University, Kusatsu, Japan
²Institute for Extra-cutting-edge Science and Technology Avantgarde Research of Life (X-star),
Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Yokosuka, Japan
Copyright Elsevier

The geochemical effects of freezing are becoming important in the investigation of closed aqueous environments, such as inland water on Earth and early Mars, and liquid water on planetesimals. Carbonate-bearing alkaline saline lakes in Mongolia are frozen in the cold season, with chemical species being partitioned among surface ice, lake water, and sediments. Freezing of the lakes leads to the accumulation of dissolved carbonate species, thereby decreasing the pH. The lakes are enriched not only in heavy metals, such as As, Mo, and U, but also in phosphorus. However, little is known about how metals and phosphorus are affected by chemical changes during freezing. Moreover, the mechanisms of major chemical changes are poorly understood and reproduced. Here we performed field surveys to investigate the behavior of these elements during lake freezing. Heavy metals and phosphorus accumulate in lake water during freezing, similar to major elements such as Cl−, with Mo and U concentrations reaching ∼1 mg/L. On the other hand, As and P accumulations are limited. Concentrations of heavy metals and phosphorus in ice increase with depth in the ice. We interpret the observed behavior using a geochemical model that accounts for their adsorption reactions coupled with water removal by freezing and carbonate precipitation. The model successfully reproduces the major chemical changes, including the decrease in pH, achieving quantitative accuracy by accounting for the combined effects of freezing and the revised solubility of carbonate minerals. The pH decrease promotes the adsorptions of As and P on sedimentary ferrihydrite particles, suppressing their accumulation in lake water. However, the decrease in pH is insufficient to promote adsorptions of Mo and U, resulting in their accumulations as major dissolved species. Adsorptions of heavy metals and phosphorus by iron oxides may be an important factor in their behaviors at low temperatures near the freezing point of water. Based on our model and observations, we discuss phosphate/carbonate precipitation in freezing porewater of icy planetesimals and phosphate availability in lake water on early Mars.

¹Valentine Megevand, ¹Sylvain Bernard, ²Corentin Le Guillou, ²Roberto Conconi, ¹François Guyot
Meteoritics & Planetary Science (in Press) Open Source Link to Article [DOI: 10.1111/maps.70214]
¹Institut de Minéralogie, Physique des Matériaux et Cosmochimie, Muséum National d’Histoire Naturelle, Centre National de la Recherche Scientifique UMR 7590, Sorbonne Université, Paris, France
²Université de Lille, CNRS, INRA, Centrale Lille, UMR 8207 – UMET – Unité Matériaux et Transformations, Villeneuve d’Ascq, France
Published by arrangement with John Wiley & Sons

Carbonaceous chondrites contain phosphorus, whose speciation and thus history remain to be investigated. Phosphorus/sulfur-bearing assemblages have been reported in carbonaceous CM chondrites, but there is no consensus about their exact compositions and origins. Here, we present submicrometer-scale investigations by analytical transmission electron microscopy of phosphorus/sulfur-bearing assemblages from the CM chondrites Murray and Murchison. Results indicate that, in CM chondrites, phosphorus associated with sulfides occurs under distinct oxidation states. In Murray, we identified a pyrrhotite–schreibersite nanocrystalline assemblage associated with carlsbergite and chromite. Its reduced nature and petrographic context are indicative of a nebular formation mechanism, possibly through kamacite sulfidation. In contrast, Murchison contains nanocrystalline pentlandite assemblages associated with carlsbergite and likely with phosphate phases that we interpret as being produced via interactions with an oxidizing fluid under asteroidal conditions. Thermodynamic modeling suggests that such complex assemblages hosting reactive forms of both phosphorus and nitrogen could promote the synthesis of activated phosphate species such as diamidophosphate, an efficient phosphorylation reagent, thereby underscoring their potential prebiotic significance.