High-precision ID-TIMS cassiterite U–Pb systematics using a low-contamination hydrothermal decomposition: implications for LA-ICP-MS and ore deposit geochronology

Cassiterite (SnO2) is the most common ore phase of Sn. Typically containing 1–100 µg g−1 of uranium and relatively low concentrations of common Pb, cassiterite has been increasingly targeted for U–Pb geochronology, principally via microbeam methods, to understand the timing and durations of granite-related magmatic–hydrothermal systems throughout geological time. However, due to the extreme resistance of cassiterite to most forms of acid digestion, there has been no published method permitting the complete, closed-system decomposition of cassiterite under conditions in which the basic necessities of measurement by isotope dilution can be met, leading to a paucity of reference and validation materials. To address this a new low blank (< 1 pg Pb) method for the complete acid decomposition of cassiterite utilising HBr in the presence of a mixed U–Pb tracer, U and Pb purification, and thermal ionisation mass spectrometry (TIMS) analyses has been developed. Decomposition rates have been experimentally evaluated under a range of conditions. A careful balance of time and temperature is required due to competing effects (e.g. HBr oxidation), yet the decomposition of 500 µm diameter fragments of cassiterite is readily achievable over periods comparable to zircon decomposition. Its acid-resistant nature can be turned into an advantage by leaching common Pb-bearing phases (e.g. sulfides, silicates) without disturbing the U–Pb systematics of the cassiterite lattice. The archetypal Sn–W greisen deposit of Cligga Head, SW England, is used to define accuracy relative to chemical abrasion–isotope dilution–thermal ionisation mass spectrometry (CA-ID-TIMS) zircon U–Pb ages and demonstrates the potential of this new method for resolving high-resolution timescales (<0.1 %) of magmatic–hydrothermal systems. However, data also indicate that the isotopic composition of initial common Pb varies significantly, both between crystals and within a single crystal. This is attributed to significant fluid–rock interactions and the highly F-rich acidic nature of the hydrothermal system. At microbeam precision levels, this issue is largely unresolvable and can result in significant inaccuracy in interpreted ages. The ID-TIMS U–Pb method described herein can, for the first time, be used to properly characterise suitable reference materials for microbeam cassiterite U–Pb analyses, thus improving the accuracy of the U–Pb cassiterite chronometer as a whole.

Highly accurate dating of micrometre-scale baddeleyite domains through combined focused ion beam extraction and U-Pb thermal ionisation mass spectrometry (FIB-TIMS)

Baddeleyite is a powerful chronometer of mafic magmatic and meteorite impact processes. High precision and accuracy U-Pb ages can be measured from single grains by isotope dilution thermal ionisation mass spectrometry (ID-TIMS), but this requires destruction of the host rock for highly challenging grain isolation and dissolution. As a result, the technique is rarely applied to precious samples with very limited availability (such as lunar, Martian and asteroidal meteorites and returned samples) or samples containing small baddeleyite grains that cannot readily be isolated by conventional mineral separation techniques. Here, we use focused ion beam (FIB) techniques, utilising both Xe+ plasma and Ga+ ion sources, to liberate baddeleyite subdomains in-situ, allowing their extraction for ID-TIMS dating. We have analysed the U-Pb isotope systematics of domains ranging between 200 um and 10 um in length and 5 ug to 0.1 ug in mass. In total, seven domains of Phalaborwa baddeleyite extracted using a Xe+-pFIB yield a weighted mean 207 Pb/206 Pb age of 2060.1 ± 2.4 Ma (0.12 %; all uncertainties 2 sigma), within uncertainty of reference values. The smallest extracted domain (ca. 10 × 15 times; 10 um) yields an internal 207 Pb/206 Pb uncertainty of ±0.15 %. Comparable levels of precision are achieved using a Ga+-source FIB instrument (±0.20 %), though the slower cutting speed limits potential application to larger grains. While the U-Pb data are between 0.5 and 13.6 % discordant, the results generate a precise upper intercept age in U-Pb concordia space of 2061.1 × 7.4 Ma; (0.72 %). Importantly, the extent of discordance does not correlate with the ratio of material to ion-milled surface area, showing that the FIB extraction does not induce disturbance of U-Pb systematics even the smallest extracted domains. Instead, we confirm the natural U-Pb variation and discordance within the Phalaborwa baddeleyite population observed with other geochronological techniques. Our results demonstrate the FIB-TIMS technique to be a powerful tool for high-accuracy in-situ U-Pb dating, which makes a wide range of targets and processes newly accessible to geochronology.

Radiogenic and stable Ce isotope measurements by thermal ionisation mass spectrometry

Techniques for the separation of Cerium (Ce) from silicate matrices and for the analysis of radiogenic (ε138Ce) and mass dependent (δ142Ce) Ce isotope variations by Thermal Ionisation Mass Spectrometry (TIMS) are presented in this study.