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Heavy metal(loid) (Cd, Co, Cr, Ni, Cu, Zn, Pb, V, Tl, and As) and Pb isotope compositions of two black shale weathering profiles were determined to investigate the geochemical behaviors of these toxic elements during black shale weathering and the heavy metal(loid) contamination and source apportionment of Pb in black shale-associated soils. Black shale has higher heavy metal(loid) concentrations than the upper continental crust and the worldwide average shale. In contrast, the surface soils have much higher heavy metal(loid) concentrations than the profile soils. The heavy metal(loid) concentrations in black shale-associated soils are higher than the Chinese and worldwide soil background values, except for Co and Pb. Black shale-associated soils, especially the surface soils, have higher average concentrations of As, Cd, Cr, Ni, Cu, and Zn than Chinese, Dutch, and Canadian soil guidelines. The enrichment factor (EF) and geoaccumulation index (I geo ) values indicate various degrees of heavy metal(loid) contamination in these soils, particularly for the heavy metals Cd, Tl, and V and metalloid As. Co and Pb contamination in these soils is not a current concern. According to the mass transfer coefficient (τ Ta,j ) values, Cd, Co, Ni, and Zn show overall losses, and other metals (Cr, Cu, Pb, and V) exhibit different behavior in the studied black shale weathering profiles. Based on a simple binary Pb isotopic mixing model, black shale is the dominant contributor to the Pb in black shale-associated soils (70.5-91.1% to profile soils and 81.2-88.8% to surface soils), and vehicle exhaust contributes less (8.9-29.5%) to the Pb in profile soils. Vehicle exhaust can exert an impact on the Pb isotopic evolution at depth intervals of 60-80 cm below the soil surface., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The tempo and magnitude of ocean oxygenation during the rise of animals in the Ediacaran Period (635 to 539 million years ago, or Ma) is debated. Reconciling this debate is key to understanding what role, if any, oxygen played in the rise of large morphologically complex life on Earth. We reconstruct a portion of Ediacaran ocean oxygenation history using thallium isotope records (reported as ε205Tl) captured in shales from South China (Wuhe section) and northwestern Canada (Goz A and Sekwi Brook sections). At first blush, our ε205Tl data from these two locations are very different. South China shales reveal two pronounced and extremely negative Tl isotope excursions, in mid-members II and III of the Doushantuo Formation (where ε205Tl authigenic reach nadirs of −10.4 ± 0.2; 2SD and − 9.1 ± 0.2; 2SD, respectively). In contrast, northwestern Canada shales reveal fairly invariant values (average ε205Tl authigenic = −2.1 ± 1.6; 2SD, n = 75). These disparate records are in much better agreement, however, if we cull from our dataset shales that were inferred in previous work to have been deposited in restricted settings. By comparison to analogous modern settings (e.g., the Black Sea), ε205Tl data in these shales most likely fingerprint local-scale processes. On the other hand, and also by comparison to modern settings (e.g., Cariaco and Santa Barbara basins), shales deposited in an open ocean setting probably captured a globally homogenous seawater ε205Tl (ε205Tl SW). Moving forward with this assumption, we find that Ediacaran open ocean ε205Tl SW values were predominantly comparable to bulk upper continental crust (ε205Tl = ~−2). These relatively heavy open ocean ε205Tl SW imply limited Mn oxide burial in global marine sediments for large periods of time during the Ediacaran, and by inference also limited accumulation of O 2 in global marine bottom waters. Only for what appear to be very brief episodes of time (≪5–10 million years) at ~635 Ma and ~580 Ma did open ocean ε205Tl SW reach values considerably lighter than bulk upper continental crust (for example, ε205Tl SW as low as −4.4 ± 0.2; 2SD at ~635 Ma and − 5.3 ± 0.3: 2SD at ~580 Ma). These much rarer negative ε205Tl SW values require short-lived episodes of globally enhanced Mn oxide burial in marine sediments, and by implication also brief episodes of enhanced accumulation of O 2 in global marine bottom waters. When interpreting geochemical data, it is important to make global-scale inferences only after identifying and accounting for local-scale overprints. Applying this strategy ourselves, we find compelling evidence for an Ediacaran global ocean that only very briefly experienced widespread bottom water oxygenation during the rise of animals. [ABSTRACT FROM AUTHOR]