Copper isotopes as a tool to trace contamination in mangroves from an urbanized watershed

This study investigates the chronology of copper (Cu) contamination and its stable isotopes within an emblematic Brazilian mangrove impacted by multiple urban and industrial Cu sources, deforestation, and eutrophication. In particular, it tests Cu isotopes as tracers of anthropogenic inputs into an anthropized watershed impacted by multiple sources. To do so, we used multi-isotopic approaches (δ⁶⁵Cu, δ¹³C, and δ¹⁵N), elemental analyses (Al, Ca, Fe, P, Cu, C, and N), and selective and sequential extractions in a²¹⁰Pb-dated sediment core. This geochemical "toolbox" allowed identifying two main stages of Cu evolution in the sediment core. In the first stage, before 1965, Cu isotope fingerprints responded to landscape changes, indicating a shift from marine to geogenic dominance due to the remobilization and erosion of terrestrial materials. In the second stage, after 1965, the sediment geochemical profile showed increased Cu total concentrations with a higher bioavailability (as reflected by sequential extraction data) accompanying changes in Cu isotope signatures towards anthropogenic values. The findings evidence that local industrial sources, possibly combined with diffuse urban sources, export Cu into downstream mangroves with a distinguishable isotope signature compared to natural values. This study demonstrates the applicability of Cu isotopes as new environmental forensic tools to trace anthropogenic sources in mangrove sediments. Incorporated into a robust geochemical toolbox that combines inorganic and organic proxies for sedimentary materials, this new tool provides a comprehensive understanding of Cu dynamics in mangrove ecosystems, shedding light on the historical and current sources of Cu.