Oscillatory Zoned Liddicoatite from Anjanabonoina, Central Madagascar. III. Trace Elements

Abstract

Abstract Large crystals of liddicoatite (tourmaline) from the Anjanabonoina Pegmatite of Central Madagascar are well-known for their distinct patterns of oscillatory zoning. This study follows two previous investigations, in which the crystal chemistry (Lussier et al. 2011a) and variations of major chemical constituents (Lussier & Hawthorne 2011) were characterized in detail. Here, the variations of elements present only at the trace level are investigated. The measurement by laser ablation inductively coupled plasma mass spectrometry of 26 trace elements, with abundances spanning four orders of magnitude (∼10−1 to 103 ppm) is reported. Trace elements were analyzed along continuous analytical traverses from the core to the rim of the crystal. Abundance profiles for most of the trace elements quantified (21 of 26) show clear oscillations that coincide with optical oscillatory zoning features. Throughout the crystal, the occurrence of compositional oscillation is independent of trace-element abundance; even where mean abundance is low, ∼1 ppm (e.g., V3+, Y3+, Th4+), oscillatory behavior is clear. Conversely, the magnitude of the oscillatory amplitude shows a strong near-linear dependence on element abundance. Within individual oscillatory zones, four unique line-shapes are observed, each differentiated by (1) the direction of a compositional discontinuity at the zone limits and (2) the orientation of the nonlinear curvature across the zone. For any individual zone, the variation in element concentration, C, can be fitted to the equation C = ±Aeλ(x−Φ)+ Δ where A is the zone amplitude; Φ is a reference position, and λi and Δi are fitted parameters. Comparison of the fitted equations shows that linear correlation between element pairs is common, occurring between pairs consisting of trace–trace, trace–major, and major–major elements. The oscillatory behavior of constituent elements is related to the location of the trace element in the tourmaline structure, with elements at the X- and Y-sites typically showing increases and decreases in abundance over single oscillatory zones. Throughout each zone, Mg has high abundance (∼104 ppm) at the start of each zone, followed by an extremely abrupt decrease in abundance, typically over a distance of <1 mm, making its behavior different to that of other elements (both trace and major). Finally, there are systematic differences in trace-element abundances between pyramid {201} and prism {100} sectors of the crystal, echoing the differences observed for major elements between these two sectors and consistent with face-dependent differences in element uptake.