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Sedimentary rocks exposed at Dob’s Linn, Scotland, have significantly influenced our understanding of how life evolved over the Ordovician to Early Silurian. The current interpreted chronostratigraphic boundary between the Ordovician and Silurian periods is a Global Boundary Stratotype Section and Point (GSSP), calibrated to 443.8 ± 1.5 Ma (Hirnatian–Rhuddanian age), based on biostratigraphic markers, radioisotopic dates and statistical modelling. However, challenges arise due to tectonic disturbances, complex correlation issues and the lack of systematic dating in Ordovician–Silurian stratigraphic sections. Here, hundreds of zircon grains from three metabentonite ash horizons were dated using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). A subset of the grains were re-analyzed using Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS). We present a high-precision CA-ID-TIMS 238U-206Pb weighted mean date of 440.44 ± 0.55/0.56/0.72 Ma (±analytical/with tracer/with U-decay constant) for the Coronagraptus cyphus biozone. However, the study reports younger, and in certain cases, older LA-ICP-MS zircon dates within the Coronagraptus cyphus, Akidograptus ascensus and Dicellograptus anceps zones, suspected as being influenced by Pb loss and LA-ICP-MS matrix mismatch. The study reports concerns about the suitability of Dob’s Linn as a GSSP section and examines various LA-ICP-MS maximum depositional age (MDA) approaches, suggesting the use of the TuffZirc date and the youngest mode weighted mean (YMWM) as suitable MDA calculations consistent with CA-ID-TIMS results.