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40Ar/39Ar dating of a hydrothermal pegmatitic buddingtonite–muscovite assemblage from Volyn, Ukraine
(2022)
We determined Ar-40/Ar-39 ages of buddingtonite, occurring together with muscovite, with the laser-ablation method. This is the first attempt to date the NH4-feldspar buddingtonite, which is typical for sedimentary-diagenetic environments of sediments, rich in organic matter, or in hydrothermal environments, associated with volcanic geyser systems. The sample is a hydrothermal breccia, coming from the Paleoproterozoic pegmatite field of the Korosten Plutonic Complex, Volyn, Ukraine. A detailed characterization by optical methods, electron microprobe analyses, backscattered electron imaging, and IR analyses showed that the buddingtonite consists of euhedral-appearing platy crystals of tens of micrometers wide, 100 or more micrometers in length, which consist of fine-grained fibers of <= 1 mu m thickness. The crystals are sector and growth zoned in terms of K-NH4-H3O content. The content of K allows for an age determination with the Ar-40/Ar-39 method, as well as in the accompanying muscovite, intimately intergrown with the buddingtonite. The determinations on muscovite yielded an age of 1491 +/- 9 Ma, interpreted as the hydrothermal event forming the breccia. However, buddingtonite apparent ages yielded a range of 563 +/- 14 Ma down to 383 +/- 12 Ma, which are interpreted as reset ages due to Ar loss of the fibrous buddingtonite crystals during later heating. We conclude that buddingtonite is suited for Ar-40/Ar-39 age determinations as a supplementary method, together with other methods and minerals; however, it requires a detailed mineralogical characterization, and the ages will likely represent minimum ages.
The metastable paragenesis of corundum and quartz is rare in nature but common in laboratory experiments where according to thermodynamic predictions aluminum-silicate polymorphs should form. We demonstrate here that the existence of a hydrous, silicon-bearing, nanometer-thick layer (called "HSNL") on the corundum surface can explain this metastability in experimental studies without invoking unspecific kinetic inhibition. We investigated experimentally formed corundum reaction products synthesized during hydrothermal and piston-cylinder experiments at 500-800 degrees C and 0.25-1.8 GPa and found that this HSNL formed inside and on the corundum crystals, thereby controlling the growth behavior of its host. The HSNL represents a substitution of Al with Si and H along the basal plane of corundum. Along the interface of corundum and quartz, the HSNL effectively isolates the bulk phases corundum and quartz from each other, thus apparently preventing their reaction to the stable aluminum silicate. High temperatures and prolonged experimental duration lead to recrystallization of corundum including the HSNL and to the formation of quartz + fluid inclusions inside the host crystal. This process reduces the phase boundary area between the bulk phases, thereby providing further opportunity to expand their coexistence. In addition to its small size, its transient nature makes it difficult to detect the HSNL in experiments and even more so in natural samples. Our findings emphasize the potential impact of nanometer-sized phases on geochemical reaction pathways and kinetics under metamorphic conditions in one of the most important chemical systems of the Earth's crust.