The use of zinc isotopes to trace anthropogenic sources in coastal areas has been tested in this study. We determined the stable isotopic composition of zinc in sediment cores, suspended particulate matter (SPM) and rocks collected at the Sepetiba Bay (southeastern Brazil), an estuarine lagoon heavily impacted by metallurgic activities.These isotopic signatures were compared with those from willemite ore, which represent the main mineral refined by the major industrial source of zinc. The aim was to test if this tracer system enables to identify sources and sinks of anthropogenic zinc and to reconstruct the temporal and spatial evolution of zinc contamination. can be useful to improve environmental monitoring efforts in coastal systems.

Precise and accurate δ 66/64 Zn data for environmental reference materials (RMs) including rocks, sediments, soils and plants are presented in order to improve the metrological traceability and analytical control of Zn isotope ratio determinations in future environmental studies. Previously developed ion exchange chromatography protocols were adjusted to enable faster sample throughput and instrumental mass bias processes were investigated. The improved chromatographic protocol yielded precise and quantitative recoveries (99 ± 7%, σ, n = 16), while the mass bias correction using Cu as external dopant provided precisions better than 0.02‰, 2σ, n = 7. Investigations into spectral and non-spectral interferences identified significant formation of Cr and Ti oxides and hydroxide ionic species. Analysis of six RMs (BHVO-2 basalt (USGS), BCR-2 basalt (USGS), AGV-2 andesite (USGS), 2709 San Joaquin soil (NIST), 1646a estuarine sediment (NIST) and 1573a tomato leaves (NIST)) showed good reproducibility (< 0.01‰, 2σ, 5 ≤ n ≥ 1).

Studies including multiple isotope systems in aerosols promises unparalleled insights into sources and pathways of metals in the atmosphere. However, such studies remain rare because of the challenges associated with small sample sizes and low analyte masses of the target elements. Here, we present the first study combining accurate and precise determination of Pb, Cu and Zn isotopic ratios in aerosols and anthropogenic materials collected in São Paulo, Brazil. We use a sequential ion chromatography procedure with two different resins for the separation and purification of the analytes. Multi collector mass spectrometry is used for the accurate and precise determination of the isotope ratios. Long term analytical reproducibilities are ±0.035 for 206Pb/204Pb, ± 0.13‰ for δ65CuNIST and ±0.1‰ for δ66ZnJMC (±2σ). Accuracy is assessed using certified reference materials (CRM NIST 2783 aerossol, BRP-1 and others). We analyzed 57 source samples (road dust, tires, cement, road tunnel aerosol) and 113 aerosol samples collected between 2013 and 2015. The results for São Paulo are critically compared with previously published data from studies conducted in São Paulo, London and Barcelona. The key findings are: 1. The isotope signatures for Zn in tires (δ66ZnJMC = 0.16 ± 0.14, 2σ, n = 9) and road dust (δ66ZnJMC = 0.17 ± 0.19, 2σ, n = 13) are similar in São Paulo and London suggesting that this isotope system can be used as element specific tracers for non-exhaust traffic. 2. 206Pb/207Pb vs δ66ZnJMC and δ66ZnJMC vs δ65CuNIST multi-isotopic diagrams successfully separate wear off from cars including tires and brakes, car exhaust, industrial emissions and cement sources and improves the discrimination of air pollutant sources. 3. The source identification based on isotope ratios agrees source apportionement based on emissions inventory from these cities. 4. We present Pb, Cu and Zn isotopic data for the first time for the CRM NIST 2783 and BRP-1. These new data will enable future intercalibration and quality controls in other laboratories. Our study confirms that stable isotope ratio analysis have a great potential for element specific source characterization (e.g., separating non combustion traffic sources from combustion sources) for Cu, Zn and Pb. Please note that this is an author-produced PDF of an article accepted for publication following peer review. The definitive publisher-authenticated version is available on the publisher Web site.

Primeros datos de isótopos de plomo en cinabrio del distrito de Geogaceta, 37 (2005), 67-70

22Atmospheric lead (Pb) concentrations in São Paulo city, Brazil, remain significant, despite the fact that leaded 23 gasoline has been phased out. The use of its isotope signature allows tracing emissions from increasing car 24 numbers, urban construction, and industrial emissions in this extremely populated area. High-precision and 25 accurate stable isotope ratio determinations using isotope dilution thermal ionization mass spectrometry (ID-26 TIMS) combined with particle induced X-ray emission (PIXE) and multivariate analysis were used to identify