Trace metal dynamics in an industrialized Brazilian river: A combined application of Zn isotopes, geochemical partitioning, and multivariate statistics.

The Paraiba do Sul (PSR) and Guandu Rivers (GR) water diversion system (120 km long) is located in the main industrial pole of Brazil and supplies drinking water for 9.4 million people in the metropolitan region of Rio de Janeiro. This study aims to discern the trace metals dynamics in this complex aquatic system. We used a combined approach of geochemical tools such as geochemical partitioning, Zn isotopes signatures, and multivariate statistics. Zinc and Pb concentrations in Suspended Particulate Matter (SPM) and sediments were considerably higher in some sites. The sediment partition of As, Cr, and Cu revealed the residual fraction (F4) as the main fraction for these elements, indicating low mobility. Zinc and Pb were mostly associated with the exchangeable/carbonate (F1) and the reducible (F2) fractions, respectively, implying a higher susceptibility of these elements to being released from sediments. Zinc isotopic compositions of sediments and SPM fell in a binary mixing source process between lithogenic (δ66/64ZnJMC ≈ + 0.30‰) and anthropogenic (δ66/64ZnJMC ≈ + 0.15‰) end members. The lighter δ66/64ZnJMC values accompanied by high Zn concentrations in exchangeable/carbonate fraction (ZnF1) enable the tracking of Zn anthropogenic sources in the studied rivers. Overall, the results indicated that Hg, Pb, and Zn had a dominant anthropogenic origin linked to the industrial activities, while As, Cr, and Cu were mainly associated with lithogenic sources. This work demonstrates how integrating geochemical tools is valuable for assessing geochemical processes and mixing source effects in anthropized river watersheds.

Behavior of metallurgical zinc contamination in coastal environments: A survey of Zn from electroplating wastes and partitioning in sediments.

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 ±â€¯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 ±â€¯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 ±â€¯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.