Tochilinite/cronstedtite intergrowths are commonly observed as alteration products in CM chondrite matrices, but the conditions under which they formed are still largely underconstrained due to their scarcity in terrestrial environments. Here, we report low temperature (80 °C) anoxic hydrothermal experiments using starting assemblages similar to the constituents of the matrices of the most pristine CM chondrite and S‐rich and S‐free fluids. Cronstedtite crystals formed only in S‐free experiments under circumneutral conditions with the highest Fe/Si ratios. Fe‐rich tochilinite with chemical and structural characteristics similar to chondritic tochilinite was observed in S‐bearing experiments. We observed a positive correlation between the Mg content in the hydroxide layer of synthetic tochilinite and temperature, suggesting that the composition of tochilinite is a proxy for the alteration temperature in CM chondrites. Using this relation, we estimate the mean precipitation temperatures of tochilinite to be 120–160 °C for CM chondrites. Given the different temperature ranges of tochilinite and cronstedtite in our experiments, we propose that Fe‐rich tochilinite crystals resulted from the alteration of metal beads under S‐bearing alkaline conditions at T = 120–160 °C followed by cronstedtite crystals formed by the reaction of matrix amorphous silicates, metal beads, and water at a low temperature (50–120 °C).

FTIR spectroscopy has been applied to NH4+-exchanged dioctahedral clay minerals to determine the molecular environment of NH4+ and to quantify N concentration. FTIR under vapourpressure control, coupled with heating and freezing treatments has shown that NH4+ ion symmetry varies with the nature of clay minerals. NH4+ has a perfect tetrahedral symmetry in hydrated or dehydrated smectites and belongs to the Td symmetry group. The NH4+-bending vibration is centred at 1450 and 1425 cm–1.The Si4+-Al3+ substitution in dioctahedral clay minerals induces the loss of symmetry elements of the NH4+ tetrahedron which acquires a C2v symmetry. As a consequence, the Td –C2v transition can be used to characterize the smectite–illite transition. Quantification of NH4+ content per half unit cell is provided by nNH4 = k[NH4]/[OH] where [NH4]/[OH] is the band area ratio of the NH4+-bending vibration to the OH-stretching vibration. k = 1.1 for hydrated smectite, 0.9 for dehydrated smectite and 0.8 for illite or tobelite. The bending vibration of NH4+ is chosen for the calculation because it is not affected by superimposed contributions.

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The cooling of steel containers in radioactive-waste storage was simulated in a step-by-step experiment from 90 to 40ºC. Among newly formed clay minerals observed in run products, cronstedtite was identified by a number of analytical techniques (powder X-ray diffraction, transmission electron microscopy, and scanning electron microscopy). Cronstedtite has not previously been recognized to be so abundant and so well crystallized in an ironÀclay interaction experiment. The supersaturation of experimental solutions with respect to cronstedtite was due to the availability of Fe and Si in solution, as a result of the dissolution of iron metal powder, quartz, and minor amounts of other silicates. Cronstedtite crystals are characterized by various morphologies: pyramidal (truncated or not) with a triangular base and conical with a rounded or hexagonal cross-section. The pyramidal crystals occur more frequently and their polytypes (2M 1 , 1M, 3T) were identified by selected area electron diffraction patterns and by automated diffraction tomography. Cronstedtite is stable within the 90À60ºC temperature range. At temperatures of 450ºC, the cronstedite crystals showed evidence of alteration.