Abstract
U–Pb dating of the common iron-oxide hematite (α-Fe2O3), using laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICP-MS), provides unparalleled insight into the timing and processes of mineral deposit formation. Until now, the full potential of this method has been negatively impacted by the lack of suitable matrix-matched standards. To achieve matrix-matching, we report an approach in which a U–Pb solution and ablated material from 99.99% synthetic hematite are simultaneously mixed in a nebulizer chamber and introduced to the ICP-MS. The standard solution contains fixed U- and Pb-isotope ratios, calibrated independently, and aspiration of the isotopically homogeneous solution negates the need for a matrix-matched, isotopically homogenous natural iron-oxide standard. An additional advantage of using the solution is that the individual U–Pb concentrations and isotope ratios can be adjusted to approximate that in the unknown, making the method efficient for dating hematite containing low (~10 ppm) to high (>1 wt %) U concentrations. The above-mentioned advantage to this solution method results in reliable datasets, with arguably-better accuracy in measuring U–Pb ratios than using GJ-1 Zircon as the primary standard, which cannot be employed for such low U concentrations. Statistical overlaps between 207Pb/206Pb weighted average ages (using GJ-1 Zircon) and U–Pb upper intercept ages (using the U–Pb mixed solution method) of two samples from iron-oxide copper-gold (IOCG) deposits in South Australia demonstrate that, although fractionation associated with a non-matrix matched standard does occur when using GJ-1 Zircon as the primary standard, it does not impact the 207Pb/206Pb or upper intercept age. Thus, GJ-1 Zircon can be considered reliable for dating hematite using LA-ICP-MS. Downhole fractionation of 206Pb/238U is observed to occur in spot analyses of hematite. The use of rasters in future studies will hopefully minimize this problem, allowing for matrix-matched data. Using the mixed-solution method in this study, we have validated a published hematite Pb–Pb age for Olympic Dam, and provide a new age (1604 ± 11 Ma) for a second deposit in the same province. These ages are further evidence that the IOCG mineralizing event is tied to large igneous province (LIP) magmatism in the region at ~1.6 Ga.
Highlights
The caveat to this is the requirement of certified matrix-matched reference materials, which do not exist for a large number of potentially dateable minerals
The present study aims at circumventing this problem by using an alternative, mixed solution–solid type of standard for U/Pb dating using LA-ICP-MS
Isotope measurements were determined using a Resonetics 193 ArF M-50 Excimer laser ablation system coupled to an Agilent 7700s ICP-MS, housed at Adelaide Microscopy, University of Adelaide
Summary
The caveat to this is the requirement of certified matrix-matched reference materials, which do not exist for a large number of potentially dateable minerals (unless it can be demonstrated that the effects of using a non-matrix-matched standard are smaller than the propagated errors). The present study aims at circumventing this problem by using an alternative, mixed solution–solid type of standard for U/Pb dating using LA-ICP-MS This concept has been tested successfully for U/Pb dating of zircon and baddeleyite [8,9,10], and non-matrix-matched trace element determination [11,12], and is here applied to dating of U-bearing hematite for the first time. The aims of this study were to: Evaluate the potential of hematite as a U–Pb geochronometer; to assess the effect of “matrix effects” when using a non-matrix matched standard, such as zircon, by comparison with the data of Ciobanu et al (2013) [3]; to test whether the method gives reliable ages for hematite with low U concentrations; and to provide an “easy-and-ready to use” method for U/Pb dating of hematite
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