Annexe A

Operating conditions for the LA-ICP-MS equipment for cassiterite analyses.

Protocole analytique LA-ICP-MS pour la cassitérite.

Laboratory & Sample Preparation
Laboratory name Géosciences Rennes, UMR CNRS 6118, Rennes, France
Sample type/mineral Cassiterite
Sample preparation In-context in thin-section and thick-section
Imaging CL: Relion CL instrument, Olympus Microscope and Leica Color Camera
Laser ablation system
Make, Model & type ESI NWR193UC, Excimer
Ablation cell ESI NWR TwoVol2
Laser wavelength 193 nm
Pulse width < 5 ns
Fluence 6 J/cm2
Repetition rate 5 Hz
Spot size 50 µm
Sampling mode/pattern Single spot
Carrier gas 100% He, Ar make-up gas and N2 (3 ml/mn) combined using in-house smoothing device
Background collection 20 s
Ablation duration 60 s
Wash-out delay 15 s
Cell carrier gas flow (He) 0.76 l/min
ICP-MS Instrument
Make, Model & type Agilent 7700x, Q-ICP-MS
Sample introduction Via conventional tubing
RF power 1350 W
Sampler, skimmer cones Ni
Extraction lenses X type
Make-up gas flow (Ar) 0.85 l/min
Detection system Single collector secondary electron multiplier
Data acquisition protocol Time-resolved analysis
Scanning mode Peak hopping, one point per peak
Detector mode Pulse counting, dead time correction applied, and analog mode when signal intensity>∼ 106 cps
Masses measured 204(Hg + Pb), 206Pb, 207Pb, 208Pb, 232Th, 238U
Integration time per peak 10–30 ms
Sensitivity / Efficiency 23 000 cps/ppm Pb (50 μm, 10 Hz)
Data Processing
Gas blank 20 s on-peak
Calibration strategy Phalaborwa Baddeleyite used as primary reference materials, Abbaretz Cassiterite used as secondary reference material (quality control)
Common-Pb correction, composition and uncertainty No common-Pb correction.
Reference Material info Phalaborwa (Heaman and Lecheminant, 1993)
Abbaretz Cassiterite (in-house)
Data processing package used Iolite 4 (Paton et al., 2011), U-Pb Geochronology (Paton et al., 2010)
Uncertainty level and propagation Ages are quoted at 2 sigma absolute, propagation is by quadratic addition according to Horstwood et al. (2016).
Quality control/Validation Abbaretz: 324.5 ± 6.5 Ma (n = 25 ; MSWD = 3.1)

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