The crystal-chemical basis for Ar retention in micas: inferences from interlayer partitioning and implications for geochronology

Cation partitioning data for coexisting muscovite and biotite are shown to be useful indicators of relative interlayer bond length/strength in these minerals. These data therefore provide a useful crystal-chemical perspective on relative mass-transfer kinetics of radiogenic isotopes, and account for the observation that biotite is generally less retentive of 40Ar and 87Sr than coexisting muscovite. Partitioning behavior of trace elements underscores three reasons why overall interlayer bonding in biotite is weaker than in muscovite. First, the preferences of large (Rb, Cs)+ in biotite and of small La3+ and Na+ in muscovite indicate a relatively spacious interlayer volume in biotite (suggesting a longer mean K−O bond). Second, the preference of interlayer vacancies in biotite (with some/all possibly H2O/H3O+-filled) suggests that its adjacent 2:1 sheets are connected by fewer interlayer bonds per unit cell than those of muscovite. Third, the relative exclusion of large Ba2+ from biotite despite its large interlayer sites is attributed to O−H bonds pointing into the interlayer cavity sub-normal to (001); (K+, Ba2+)-H+ repulsion thereby induced by the bare proton both destabilizes Ba2+ and weakens K−O bonds. In contrast, muscovite offers a more favorable electrostatic environment for Ba2+ substitution since its O−H bonds are directed into the vacant M1 octahedral site sub-parallel to (001). This hypothesis is supported by the observation that progressive F(OH)−1 exchange enhances Ba2+ partitioning into biotite/phlogopite relative to coexisting muscovite. These crystal-chemical differences between biotite and muscovite are mirrored in calculated values of “ionic porosity”, Z i , defined here as the percentage of their interlayer unit-cell volume not occupied by ions. A monitor of ionic packing density and geometry, Z i is inversely correlated with K−O bond strength, which appears to be the rate-determining “kinetic common denominator” for a variety of processes affecting micas – including those responsible for loss of radiogenic isotopes in biotite and muscovite. Accordingly, the relatively longer/weaker K−O bonds of biotite are envisioned as being more easily stretched (during volume diffusion) or broken (during recrystallization or retrograde alteration). This in turn accounts for common observations of enhanced radiogenic Ar/Sr loss and younger 40Ar/39Ar and Rb/Sr ages in natural biotite (high Z i ) relative to coexisting muscovite (lower Z i ). Significantly, this pattern may arise irrespective of isotopic loss mechanism (diffusion or recrystallization, etc.), and it follows that any age discordance observed between muscovite and biotite cannot be ascribed uniquely to one mechanism or the other without appropriate field, petrographic, and petrologic constraints. Extension of this partitioning/porosity-based synthesis leads to prediction of corollary age-retentivity-composition effects among chemically diverse trioctahedral and dioctahedral micas, which are best field tested in terranes that cooled slowly under dry, static conditions. Pressure effects on argon retention are also inferred from the porosity model.