Abstract 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 Sao 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 Sao Paulo are critically compared with previously published data from studies conducted in Sao 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 Sao 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 apportionment 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.

中文翻译：

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城市气溶胶和人为源中 Pb、Cu 和 Zn 的多同位素方法改善了特大城市大气污染物源的追踪

摘要 包括气溶胶中多种同位素系统的研究有望对大气中金属的来源和途径提供无与伦比的见解。然而，由于样本量小和目标元素分析物质量低等挑战，此类研究仍然很少见。在这里，我们展示了第一项结合准确和精确测定气溶胶和在巴西圣保罗收集的人为材料中的铅、铜和锌同位素比率的研究。我们使用连续离子色谱程序和两种不同的树脂来分离和纯化分析物。多收集器质谱法用于准确和精确测定同位素比率。206Pb/204Pb 的长期分析重现性为 ±0.035，δ65CuNIST 为 ±0.13‰，δ66ZnJMC 为 ±0.1‰ (±2σ)。使用经认证的参考材料（CRM NIST 2783 气溶胶、BRP-1 等）评估准确性。我们分析了 2013 年至 2015 年期间收集的 57 个源样本（道路灰尘、轮胎、水泥、公路隧道气溶胶）和 113 个气溶胶样本。将圣保罗的结果与之前在圣保罗、伦敦和巴塞罗那进行的研究中公布的数据进行了严格比较。主要发现是： 1. 轮胎中锌 (δ66ZnJMC = 0.16 ± 0.14, 2σ, n = 9) 和道路灰尘 (δ66ZnJMC = 0.17 ± 0.19, 2σ, n = 13) 的同位素特征在圣保罗和伦敦相似表明该同位素系统可用作非排气流量的元素特定示踪剂。2. 206Pb/207Pb 与 δ66ZnJMC 和 δ66ZnJMC 与 δ65CuNIST 多同位素图成功地将磨损与汽车（包括轮胎和制动器、汽车尾气、工业排放和水泥源，提高大气污染源的判别能力。3. 基于同位素比的源识别与基于这些城市排放清单的源分配一致。4. 我们首次提供了 CRM NIST 2783 和 BRP-1 的 Pb、Cu 和 Zn 同位素数据。这些新数据将使未来其他实验室的相互校准和质量控制成为可能。我们的研究证实，稳定同位素比分析对于 Cu、Zn 和 Pb 的元素特定源表征（例如，将非燃烧交通源与燃烧源分开）具有很大的潜力。首次获得 CRM NIST 2783 和 BRP-1 的 Cu 和 Zn 同位素数据。这些新数据将使未来其他实验室的相互校准和质量控制成为可能。我们的研究证实，稳定同位素比分析对于 Cu、Zn 和 Pb 的元素特定源表征（例如，将非燃烧交通源与燃烧源分开）具有很大的潜力。首次获得 CRM NIST 2783 和 BRP-1 的 Cu 和 Zn 同位素数据。这些新数据将使未来其他实验室的相互校准和质量控制成为可能。我们的研究证实，稳定同位素比分析对于 Cu、Zn 和 Pb 的元素特定源表征（例如，将非燃烧交通源与燃烧源分开）具有很大的潜力。