HTP21/c–C2/c phase transition and kinetics of Fe2+–Mg order–disorder of an Fe-poor pigeonite: implications for the cooling history of ureilites

A natural Ca-poor pigeonite (Wo₆En₇₆Fs₁₈) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2₁/c, was annealed up to 1,093°C to induce a phase transition from P2₁/c to C2/c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections (h + k = 2n + 1, present only in the P2₁/c phase) showed a displacive phase transition P2₁/c to C2/c at a transition temperature T _Tr = 944°C, first order in character. The Fe–Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe–Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k _D versus 1/T yielded the following equation: ln k_\textD = - 3717( ±416)/T(K) + 1.290( ±0.378);    (R² = 0.988) \ln \,k_{\text{D}} = - 3717( \pm 416)/T(K) + 1.290( \pm 0.378);\quad (R^{2} = 0.988) . The closure temperature (T _c) calculated using this equation was ∼740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe–Mg degree of order, performed according to Mueller’s model, allowed us to retrieve the disordering rate constants C ₀ K _dis⁺ for all three temperatures yielding the following Arrhenius relation: ln( C₀ K_\textdis ⁺ ) = ln K₀ - Q/(RT) = 20.99( ±3.74) - 26406( ±4165)/T(K);    (R² = 0.988) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = \ln \,K_{0} - Q/(RT) = 20.99( \pm 3.74) - 26406( \pm 4165)/T(K);\quad (R^{2} = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe–Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X _Fe (in the range of X _Fe = 0.20–0.50): ln( C₀ K_\textdis ⁺ ) = (21.185 - 1.47X_\textFe ) - \frac(27267 - 4170X_\textFe )T(K) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = (21.185 - 1.47X_{\text{Fe}} ) - {\frac{{(27267 - 4170X_{\text{Fe}} )}}{T(K)}} . The cooling time constant, η = 6 × 10⁻¹ K⁻¹ year⁻¹ calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.