Fingerprinting Fluid Source in Calcite Veins: Combining LA-ICP-MS U-Pb Calcite Dating with Trace Elements and Clumped Isotope Palaeothermometry

Abstract

Application of geochemical proxies to vein minerals - particularly calcite - can fingerprint the source of fluids controlling various important geological processes from seismicity to geothermal systems. Determining fluid source, e.g. meteoric, marine, magmatic or metamorphic waters, can be challenging when using only trace elements and stable isotopes as different fluids can have overlapping geochemical characteristics, such as δ18O. In this contribution we show that by combining the recently developed LA-ICP-MS U-Pb calcite geochronometer with stable isotopes (including clumped isotope palaeothermometry) and trace element analysis, the fluid source of veins can be more readily determined. Calcite veins hosted in the Devonian Montrose Volcanic Formation at Lunan Bay in the Midland Valley Terrane of Central Scotland were used as a case study. δD values of fluid inclusions in the calcite, and parent fluid δ18O values reconstructed from clumped isotope palaeothermometry, gave values which could represent a range of fluid sources: metamorphic or magmatic fluids, or surface waters which had undergone much fluid-rock interaction. Trace elements showed no particularly distinctive patterns. LA-ICP-MS U-Pb dating determined the vein calcite precipitation age – 318±30 Ma – indicating a metamorphic or magmatic fluid source was unlikely as there was no metamorphic or magmatic activity was occurring in the area at this time. The vein fluid source was therefore interpreted to be a surface water (meteoric based on paleogeographic reconstruction) which had undergone significant water-rock interaction. This study highlights the importance of combining the recently developed LA-ICP-MS U-Pb calcite geochronometer with stable isotopes and trace elements to help determine fluid sources of veins, and indeed any geological feature where calcite precipitated from a fluid that may have resided in the crust for a period of time (e.g. fault precipitates or cements).