Crystal chemistry of volcanic allanites indicative of naturally induced oxidation-dehydrogenation

The crystal chemistry of volcanic allanites from both the Youngest Toba Tuff (YTT), Sumatra, Indonesia and SK100 volcanic ash beds (SK100-VAB), Niigata, Japan has been examined by electron microprobe analysis (EMPA), Fourier-transform infrared spectroscopic analysis (FTIR), and single-crystal structure analysis. In the FTIR study, based on the Diamond ATR accessory, YTT and SK100- VAB allanites were observed to have different OH contents, respectively: the former has 0.64 wt% H₂O (OH: 0.40 apfu.), while the latter has 1.65 wt% H₂O (OH: 1.00 apfu.). The crystal structures of these two allanites have been refined to individual R indices (3.64 and 4.25) based on 1350 observed reflections (|Fo| > 4sig|Fo|) measured using a single-crystal diffractometer with MoKα X-radiation. The OH-poor YTT allanite has a shorter b axis, a longer c axis, and larger β value than the relatively OH-rich SK100-VAB one. The bond valence sums of O4 (accepter oxygen for H atom) and O10 (donor oxygen for H atom) are 1.962 and 1.709 v.u. for YTT allanite (valence sum: 3.671 v.u.) and 1.754 and 1.271 v.u. for SK100-VAB one (valence sum: 3.025 v.u.). The difference from the ideal total bond valence value (4.00 v.u.) of O4 and O10 in YTT allanite (0.33 v.u.) is smaller than that in SK100-VAB (0.98 v.u.). These difference values are also broadly consistent with the corresponding differences in OH content between the YTT (OH: 0.40 apfu.) and SK100-VAB allanites (OH: 1.00 apfu.) determined by FTIR- ATR. Chemical analyses, FTIR-ATR and crystal structure refinement of YTT and SK100-VAB allanites yielded the following crystal chemical formula: YTT: (Ca_0.83Mn²⁺ _0.06Fe²⁺ _0.11)(La_0.24Ce_0.32Pr_0.04Nd_0.11Sm_0.02Th_0.04Ca_0.21)(Al_0.73Fe³⁺ _0.19Ti_0.08)(Al_0.89Fe³⁺ _0.11)(Fe²⁺ _0.22Fe³⁺ _0.62Mg_0.16)(SiO₄)Si₂O₇O_1.6(OH)_0.4, SK100-VAB: (Ca_0.81Fe²⁺ _0.13Mn²⁺ _0.06)(La_0.22Ce_0.34Pr_0.05Nd_0.13Sm_0.02Th_0.02Ca_0.22)(Al_0.76Fe³⁺ _0.19Ti_0.05)Al_1.00(Fe²⁺ _0.73Fe³⁺ _0.17Mg_0.10)(Si_0.96Al_0.04O₄)Si₂O₇O(OH). Therefore, it is concluded that welding of the Youngest Toba Tuff caused the following post-crystallization changes to occur in YTT allanite: oxidation of Fe²⁺ to Fe³⁺, release of H₂, and the concomitant replacement of OH^? by O^2?. These oxidation and dehydrogenation processes advanced during the welding to thereby produce oxyallanite. Oxyallanite had been reported only in laboratory studies where it was produced by heating natural allanite. Our report on natural oxyallanite suggests that it may be present in other welded silicic volcanic rocks as well.