Metasomatic alteration of zircon at lower crustal P-T conditions utilizing alkali- and F-bearing fluids: Trace element incorporation, depletion, and resetting the zircon geochronometer

Abstract

Natural alteration of zircon takes place in melts or fluids either via dissolution coupled with overgrowth or via a coupled dissolution-reprecipitation process. The latter results in the zircon being partially or totally replaced by new, compositionally re-equilibrated zircon or a new mineral phase or both. In this study, fragments (50–300 μm) from a large, inclusion-free, clear, 520–530 Ma euhedral zircon with light radiation damage from a nepheline syenite pegmatite, Seiland Igneous Province, northern Norway, were experimentally reacted in 20 mg batches with 5 mg of ThO2 + ThSiO2 + SiO2 and a series of alkali-bearing fluids in sealed Pt capsules at 900 °C and 1000 MPa for 6–11 days in the piston cylinder press using a CaF2 setup with a cylindrical graphite oven. ThO2 + ThSiO2 + SiO2 was present at the end of the experiment. In experiments involving H2O, H2O + NaCl, H2O + KCl, and 2 N KOH, no reaction textures formed other than a slight dissolution of the zircon grain fragments. Experiments involving 2 N NaOH, Na2Si2O5 + H2O, and NaF + H2O resulted in zircon reaction textures with varying degrees of intensity, which took the form of partial replacement by compositionally modified zircon via a coupled dissolution-reprecipitation process. In the NaF + H2O experiment some overgrowth also occurred. Altered zircon is separated by sharp compositional boundaries from unaltered zircon. Secondary ion mass spectrometry (SIMS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis indicates that, relative to the unaltered zircon, the altered zircon is strongly enriched in Th, and heavily to moderately depleted in U and (Y + REE). In all the experiments, 206Pb (3–5 ppm in unaltered zircon) is depleted in the altered zircon to below the SIMS detection limit and to at or below the LA-ICP-MS detection limit. Hafnium and Ti concentrations in the altered zircon retained the same approximate value (within error) as the original zircon. The results from these experiments demonstrate that zircon can be compositionally modified by alkali-bearing and alkali-F-bearing fluids via a coupled dissolution-reprecipitation process. Near to total loss of radiogenic Pb via such processes under high-grade conditions resets the internal zircon geochronometer. Although the end result is the same as with zircon overgrowth, i.e. the production of new generation zircon at the time of a metamorphic/metasomatic event, such replacement processes can explain incomplete isotopic ‘resetting’; inclusion production through unmixing of solid solutions in metastable zircon compositions; and ‘ghost’ textures that preserve initial growth features but with isotopic disturbance. Diagnostic replacement features produced in experiments, such as interface geometries between altered and unaltered zircon, provide markers of the mechanism and aid in zircon interpretation. A major implication from this study is that if zircon with low radiation damage can be metasomatically altered under high-grade conditions, this would have important consequences with respect to zircons presumed role as an impregnable container for mineral inclusions. Namely the mineral inclusions contained within zircon could also be altered, reset as a geochronometer, or even replaced by another mineral.