The Effects of Retrograde Reactions and of Diffusion on 40Ar-39Ar Ages of Micas

The effects of metamorphic reactions occurring during decompression were explored to understand their influence on the 40Ar-39Ar ages of micas. Monometamorphic metasediments from the Lepontine Alps (Switzerland) reached lower amphibolite facies during the Barrovian metamorphism related to the collision between European and African (Adria) continental plates. Mineral assemblages typically composed of garnet, plagioclase, biotite, muscovite and paragonite (or margarite) were screened for petrological equilibrium, to focus on samples that record a minimum degree of retrogression. X-ray diffraction data indicate that some mineral separates prepared for 40Ar-39Ar stepwise heating analysis are monomineralic, whereas others are composed of two white micas (muscovite with paragonite or margarite), or biotite and chlorite. In monomineralic samples 37Ar/39Ar and 38Ar/39Ar (proportional to Ca/K and Cl/K ratios) did not change and the resulting ages can be interpreted unambiguously. In mineral separates containing two white micas, Ca/K and Cl/K ratios were variable, reflecting non-simultaneous laboratory degassing of the two heterochemical Ar reservoirs. These ratios were used to identify each Ar reservoir and to unravel the age. In a chlorite-margarite-biotite calcschist equilibrated near 560°C and 0·65 GPa, biotite, margarite, and muscovite all yield ages around 18 Ma. At slightly higher grade (560-580°C, 0·8-0·9 GPa), the assemblage muscovite-paragonite-plagioclase is in equilibrium and remains stable during retrogression. In this case, muscovite and paragonite yield indistinguishable ages around 16·5 Ma. Above 590°C, paragonite was mostly consumed to form plagioclase >590°C, whereby the relict mica yields an age up to 5·6 Ma younger than muscovite. This partial or total resetting of the Ar clock in paragonite is interpreted to reflect plagioclase growth during decompression. Where biotite is present within this same assemblage, it systematically yields a younger age than muscovite, by 0·5-2 Ma. However, these biotites all show small amounts of retrograde chlorite formation. We conclude that even very minor chloritization of biotite is apparently a more effective process than temperature in resetting the Ar clock, as is the formation of plagioclase from paragonite decomposition. Multi-equilibrium thermobarometry is an excellent means to ensure that equilibrium in investigated samples is preserved, and this helps to obtain geologically meaningful metamorphic ages. However, even samples passing such equilibrium tests may still show retrograde effects that affect the Ar retention of micas. A more robust interpretation of such 40Ar-39Ar results may require use of a second geochronometer, such as U-Pb on monazit