Zircon as a provenance tracer: Coupling Raman spectroscopy and Usingle bondPb geochronology in source-to-sink studies

Usingle bondPb zircon geochronology is one of the most widely used techniques in sedimentary provenance analysis. Unfortunately, the ability of this method to identify sediment sources is often degraded by sediment recycling and mixing of detritus from different source rocks sharing similar age signatures. These processes create non-unique zircon Usingle bondPb age signatures and thereby obscure the provenance signal. We here address this problem by combining detrital zircon Usingle bondPb geochronology with Raman spectroscopy. The position and width of the Raman signal in zircon scales with its degree of metamictization, which in turn is sensitive to temperature. Thus, combined U-Pb + Raman datasets encode information about the crystallization history of detrital zircons as well as their thermal history. Using three borehole samples from Mozambique as part of a source-to-sink study of interest for hydrocarbon exploration, we show that zircon populations with similar Usingle bondPb age distributions can exhibit different Raman signatures. The joint U-Pb + Raman analysis allowed us to identify three different annealing trends, which were linked to specific thermal events. Thus we were able to differentiate a dominant Pan-African Usingle bondPb age peak into several sub-populations and highlight the major effect of Karoo tectono-magmatic events. In our case study, we used Raman also as a means to systematically identify all zircon grains in heavy-mineral mounts, resulting in considerable time savings. Raman spectroscopy is a non-destructive and cost-effective method that is easily integrated in the zircon Usingle bondPb dating workflow to augment the resolution power of detrital zircon Usingle bondPb geochronology

Alluvial record of an early Eocene hyperthermal within the Castissent Formation, the Pyrenees, Spain

The late Palaeocene to the middle Eocene (57.5 to 46.5 Ma) recorded a total of 39 hyperthermals – periods of rapid global warming documented by prominent negative carbon isotope excursions (CIEs) as well as peaks in iron content – have been recognized in marine cores. Documenting how the Earth system responded to rapid climatic shifts during hyperthermals provides fundamental information to constrain climatic models. However, while hyperthermals have been well documented in the marine sedimentary record, only a few have been recognized and described in continental deposits, thereby limiting our ability to understand the effect and record of global warming on terrestrial systems. Hyperthermals in the continental record could be a powerful correlation tool to help connect marine and continental deposits, addressing issues of environmental signal propagation from land to sea. In this study, we generate new stable carbon isotope data (δ13C values) across the well-exposed and time-constrained fluvial sedimentary succession of the early Eocene Castissent Formation in the south central Pyrenees (Spain). The δ13C values of pedogenic carbonate reveal – similarly to the global records – stepped CIEs, culminating in a minimum δ13C value that we correlate with the hyperthermal event “U” at ca. 50 Ma. This general trend towards more negative values is most probably linked to higher primary productivity leading to an overall higher respiration of soil organic matter during these climatic events. The relative enrichment in immobile elements (Zr, Ti, Al) and higher estimates of mean annual precipitation together with the occurrence of small iron oxide and iron hydroxide nodules during the CIEs suggest intensification of chemical weathering and/or longer exposure of soils in a highly seasonal climate. The results show that even relatively small-scale hyperthermals compared with their prominent counterparts, such as PETM, ETM2, and ETM3, can leave a recognizable signature in the terrestrial stratigraphic record, providing insights into the dynamics of the carbon cycle in continental environments during these events