Abstract
The contamination of coastal environments by metallurgical wastes involves multiple biogeochemical processes; accordingly, understanding metal behavior and risk evaluation of contaminated areas, such as Sepetiba Bay (Rio de Janeiro, Brazil), remains challenging. This study coupled Zn isotopic analyses with sequential extractions (BCR) to investigate the mechanisms of Zn transfer between legacy electroplating waste and the main environments in Sepetiba Bay. This metallurgical waste showed a light bulk isotopic signature (δ66/64ZnbulkJMC = +0.30 ± 0.01‰, 2 s, n = 3) that was not distinct from the lithogenic geochemical baseline, but was different from signature of mangrove sediment considered as anthropogenic end member (δ66/64ZnJMC = +0.86 ± 0.15‰) in a previous isotopic study in this area. Zn isotopic compositions of sediment samples (ranging from +0.20 to +0.98‰) throughout the bay fit a mixing model involving multiple sources, consistent with previous studies. In the metallurgic zone, the exchangeable/carbonate fraction (ZnF1) exhibited high Zn concentrations (ZnF1 = 9840 μg g-1) and a heavy isotopic composition (δ66/64ZnF1JMC = +1.10 ± 0.01‰). This finding showed that, in some cases, the bulk isotopic signature of waste is not the most relevant criterion for evaluating trace metal dispersion in the environment. Indeed, based on the BCR, it was observed that part of the anthropogenic metallurgical Zn was redistributed from the exchangeable/carbonate fraction in the waste to the surrounding mangrove sediment. Then, this contaminated sediment with heavy δ66/64Zn values was exported to other coastal environments. In Sepetiba Bay, contaminated sediments revealed a large concentration of ZnF1 fraction (up to 400 μg g-1) with a heavy Zn isotopic signature. This signature also matched the Zn isotopic signature of oysters in Sepetiba Bay reported by other studies; hence, measurement of the isotopic exchangeable/carbonate fraction has important implications for tracing the transfer of anthropogenic Zn to biota.