In-situ LuHf geochronology of garnet, apatite and xenotime by LA ICP MS/MS

• Published in: Chemical geology 2021-09, Vol.577, Article 120299
• Main Authors: Simpson, Alexander, Gilbert, Sarah, Tamblyn, Renee, Hand, Martin, Spandler, Carl, Gillespie, Jack, Nixon, Angus, Glorie, Stijn
• Format: Article
• Language: English
• Subjects: Apatite; Garnet; Geochronology; In situ; LA-ICP-MS; LA-ICP-MS/MS; LAQQQ-ICP-MS; Lu-Hf; Xenotime
• ISSN: 0009-2541; 1872-6836
• DOI: 10.1016/j.chemgeo.2021.120299

LuHf geochronology is a powerful method to constrain the temporal evolution of geological systems. Traditional application of this dating method requires time-consuming chemical separation of the parent (176Lu) and daughter (176Hf) isotopes that is commonly accompanied by loss of textural context of the analysed minerals. In contrast, In-situ (laser-ablation based) LuHf geochronology offers a number of advantages including rapid analysis with high spatial resolution, as well as control on textural relationships of the analysed mineral. However, laser-ablation based LuHf geochronology has been hindered by isobaric interferences of 176Yb and 176Lu on 176Hf that have effectively masked reliable determination of 176Lu and 176Hf. We present a methodology that resolves these interferences using LA-ICP-MS/MS (laser ablation tandem inductively coupled mass spectrometry) and NH3 gas to separate Hf from Lu. Both Lu, Yb, and Hf react with NH3 to form a variety of product ions. By measuring high order reaction products (e.g. Hf(NH)(NH2)(NH3)3+), we demonstrate that 176Hf can be measured interference-free from 176Lu and 176Yb with sufficient sensitivity to yield useful geochronological age data. The novel in-situ LuHf technique has been successfully applied to a variety of Palaeozoic and Precambrian-aged garnet, apatite and xenotime samples, including published reference materials. The resulting age uncertainties are as low as ~0.5% (95% conf. interval). The technique has the potential to obtain spatially-resolved LuHf ages in garnet-bearing samples that would be difficult to obtain by conventional techniques. The method also offers the opportunity for rapid “campaign style” geochronology in complex terrains that record poly-metamorphic histories. In apatite, the expected higher closure temperature of the LuHf system compared to the commonly used UPb system allows high-temperature thermal history reconstructions. In addition, LuHf dating of apatite allows dating of samples with low U and high common Pb (e.g. mafic and low-grade metamorphic rocks and ore deposits). Furthermore, apatite tends to incorporate little to no common Hf, allowing single grain ages to be calculated, which opens new doors for detrital provenance studies. In situ LuHf dating of xenotime offers an additional avenue to UPb dating, and may be particularly beneficial to dating of rare earth element ore deposits that often have complex temporal records of development.