Interrogating trees for isotopic archives of atmospheric sulphur deposition and comparison to speleothem records

Palaeorecords which depict changes in sulphur dynamics form an invaluable resource for recording atmospheric pollution. Tree rings constitute an archive that are ubiquitously available and can be absolutely dated, providing the potential to explore local- to regional-scale trends in sulphur availability. Rapid isotopic analysis by a novel "on-line" method using elemental analyser isotope ratio mass spectrometry (EA-IRMS) is developed, achieving sample precision of <0.4‰ using sample sizes of 40 mg wood powder. Tree cores from NE Italy show trends in pollution, evidenced through increasing concentrations of sulphur towards the youngest growth, and inverse trends in sulphur isotopes differentiating modern growth with light sulphur isotopes (+0.7‰) from pre-industrial growth (+7.5‰) influenced by bedrock composition. Comparison with speleothem records from the same location demonstrate replication, albeit offset in isotopic value due to groundwater storage. Using EA-IRMS, tree ring archives form a valuable resource for understanding local- to regional-scale sulphur pollution dynamics. - Highlights: • Sulphur isotopes from tree rings are analysed using 'on-line' EA combustion. • Isotopes differentiate modern growth influenced by pollution from pre-industrial growth. • Biogeochemical cycling imparts minimal delay in sulphur incorporation into tree rings. • Trends in pollution are replicated between speleothems and trees from the same location. - Sulphur isotopes extracted from tree ring records are used to identify twentieth century pollution dynamics at the local- to regional-scale