Rehydroxylation of the previously dehydroxylated dioctahedral 2:1 layer clay mineral occurs preferentially in specific sites within the former octahedral sheet. The rehydroxylation of dehydroxylated Al-rich and Al,Mg-rich 2:1 layers occurs as trans-vacant (tv) structural arrangements, regardless of whether the initial structure was tv or cis-vacant (cv). In nontronite (Fe-rich 2:1 layer clay), the dehydroxylate pseudo-cv structure is probably directly reconstructed into the rehydroxylated cv structure without migration of octahedral cations. Rehydroxylation occurs preferentially in the R3+-Or-R3+ former octahedral structural arrangements (Or = residual oxygen) over R2+-Or-R (R = R3+ or R2+ = Al3+, Fe3+ or Mg2+, Fe2+). In the case of the R2+ octahedral substitution, the interlayer cation is attracted to the electrostatically undersaturated residual oxygen of the R2+-Or-R arrangement, which blocks the ability of water molecules to pass through the ditrigonal cavity and rehydroxylate the previously dehydroxylated local arrangement. The pyrophyllite-like type of octahedral R3+-Or-R3+ arrangements, formed due to the lack of tetrahedral substitution and resulting in the absence of interlayer cations, is thus favored for rehydroxylation over the mica-like R3+-Or-R3+ arrangements where Al occurs in the tetrahedral sheet. The valence of the interlayer cation and the charge density of the 2:1 layer clay mineral, which controls the interlayer cation content, also affect the degree of rehydroxylation.

Dehydroxylated 2:1 layer minerals with a high-rehydroxylation potential, including beidellite and illite, use all the adsorbed water molecules that persist above 200 °C for rehydroxylation; the water vapor from the ambient environment also becomes a source of H2O molecules for rehydroxylation. The high demand for water molecules to use for rehydroxyltion results in a noticeable gain of mass in the temperature interval between 200 and 350 °C even during heating.

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