Dolomite dissolution: An alternative diagenetic pathway for the formation of palygorskite clay

Palygorskite is a fibrous, magnesium‐bearing clay mineral commonly associated with Late Mesozoic and Early Cenozoic dolomites. The presence of palygorskite is thought to be indicative of warm, alkaline fluids rich in Si, Al and Mg. Palygorskite has been interpreted to form in peritidal diagenetic environments, either as a replacement of detrital smectite clay during a dissolution–precipitation reaction or solid‐state transformation, or as a direct precipitate from solution. Despite a lack of evidence, most diagenetic studies involving these two minerals posit that dolomite and palygorskite form concurrently. Here, petrological evidence is presented from the Umm er Radhuma Formation (Palaeocene–Eocene) in the subsurface of central Qatar for an alternative pathway for palygorskite formation. The Umm er Radhuma is comprised of dolomitized subtidal to peritidal carbonate cycles that are commonly capped by centimetre‐scale beds rich in palygorskite. Thin section, scanning electron microscopy and elemental analyses demonstrate that palygorskite fibres formed on both the outermost surfaces of dissolved euhedral dolomite crystals and within partially to completely dissolved dolomite crystal cores. These observations suggest that dolomite and palygorskite formed sequentially, and support a model by which the release of Mg²⁺ ions and the buffering of solution pH during dolomite dissolution promote the formation of palygorskite. This new diagenetic model explains the co‐occurrence of palygorskite and dolomite in the rock record, and provides valuable insight into the specific diagenetic conditions under which these minerals may form.     

Sub-Micrometre Resolution FIB-SEM-based ToF-SIMS Used to Map Geochemical Zoning in Four Zircon Reference Materials

Zircon geochemistry can vary over micrometre scales; therefore, natural reference materials need to be well characterised before being used to calculate trace element mass fractions in unmeasured samples. Moreover, reference material homogeneity needs to be ensured with the accelerating rate of geoanalytical developments to map mineral chemistry at increasingly finer scales. Here, we investigate trace element zoning in four widely used zircon reference materials: 91500, Mud Tank, Temora and Plešovice, as well as zircon crystals from the Mount Dromedary/Gulaga Igneous Complex, Australia. Sub-micrometre resolution focused ion beam scanning electron microscope (FIB-SEM) based time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 5 μm resolution LA-ICP-MS mapping show that trace elements are zoned in all reference materials, though 91500 exhibited the least zonation. We demonstrate that FIB-SEM-based ToF-SIMS can rapidly resolve variations in trace elements (e.g., U, Th, Sc, Y, Gd, Dy, Yb and Li) at sensitivities down to the μg g^-1 level with a spatial resolution of 195 nm for areas 100 × 85 μm to 959 × 828 μm. Zircon 91500 is recommended for future quantitative analyses provided that (1) the spatial distribution of elements is imaged before analysis of unknown samples and (2) it is used in conjunction with a doped glass as the primary reference material.