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Black shales represent one of the main reservoirs of metals released to hydrosphere via chemical weathering and play an important role in geochemical cycling of metals in the ocean. The stable isotope systematics of transitional metals (e.g., Cu and Zn) may be used as a proxy for evaluating their geochemical cycling. To investigate the behaviors of Cu and Zn isotopes during metal enrichment of black shales and the migration during weathering, in this study we reported Cu and Zn concentration and isotope data for unweathered and weathered metalliferous shales and siliceous interbeds from the Maokou Formation in central China. The unweathered shales and cherts have moderately enriched Cu and Zn concentrations with silicate-like δ 65 Cu (+ 0.14 ± 0.09‰, 1σ) but heavy δ 66 Zn (0.51 ± 0.11‰, 1σ). The elevated δ 66 Zn values reflect an important contribution from seawater via sulfide precipitation and/or organic matter (OM) adsorption. The Zn isotopic compositions of these metalliferous shales are different from those of the ‘normal’ shales, highlighting the potential of Zn isotopes as a tracer for metal enrichment in natural systems. The weathered shales and cherts have an extreme δ 65 Cu range from − 6.42‰ to + 19.73‰ and a modest δ 66 Zn range of + 0.25‰ to + 0.78‰. The strongly weathered samples have lower Cu and Zn concentrations and lighter isotopic compositions compared to the weakly weathered samples. The leaching of Cu- and Zn-rich sulfides in shallow depths and their downward transport and refixation by Fe-sulfide account for the Cu and Zn isotope fractionation, with the huge Cu isotope variation generated by multistage redox leaching. In general, δ 66 Zn values of the weathered shales shift towards light values compared to the unweathered protoliths, suggesting that shale weathering releases Zn which is isotopically heavier than igneous rocks and the global riverine average (+ 0.33‰). Our results therefore indicate that Cu isotopes can be extremely fractionated during weathering of Cu-rich shales and both heavy Cu and Zn isotopes are preferentially released into fluids during shale weathering. These results should be considered when evaluating geochemical cycling of Cu and Zn in the modern or past oceans. [ABSTRACT FROM AUTHOR]

Paddy soils around mining areas suffer from the great threat of heavy metal pollution. The traditional source-tracing methods based on metal concentrations limit our ability to quantify the sources of heavy metals and trace their transport processes to paddy soils. In this study, Zn isotope compositions of paddy soils in Dabaoshan mine area, a typical sulfide deposit in southern China, have been systematically studied. According to a plot between 1/Zn (i.e. inverse concentration) and δ66Zn value, all the polluted paddy soils fall on the mixing line between acid mine drainage precipitate (AMD-precipitate) and fertilizer while the unpolluted paddy soil falls on the mixing line between fertilizer and bedrock. This indicates the mixing of Zn sources at least three end-members: the mining end-member (i.e. AMD-precipitate), the agricultural end-member (i.e. fertilizer), and bedrock whose geochemical signature is often overprinted by the former two sources around the mining area. The quantitative calculations to apportion the end-member's contributions show that the mining activity contributes most Zn in the paddy soils with an average of ∼66.2%. The contribution of mining activities has significant spatial variations. Specifically, the mining activities have relatively low impacts on the lower reach and the deep soil. Additionally, the apparent Zn isotope fractionation between AMD and AMD-precipitate (Δ66Zn AMD-precipitate − AMD of −0.35 to −0.08‰) in the tailings dam suggests that Zn cations in AMD coprecipitated with the secondary Fe-bearing minerals (e.g. jarosite and goethite). After being discharged from the tailings dam, Zn is mainly carried by the Fe-oxide minerals and migrated during surface runoff. Our study highlights the contribution of human activities to the Zn pollution in the paddy soils and the key role of Fe-bearing minerals in the migration of Zn. These findings provide a scientific base for the development of policy for pollution control in mining-affected region. Image 1 • Zn isotope compositions in paddy soils and other environmental media were examined. • Mining activities contributed 66.2% of Zn to paddy soils. • Zn was mainly carried by the Fe-bearing minerals during migration in mining area. • Zn isotope is a powerful source tracer in a complex mining-affected area. Mining activities are the main Zn source in the paddy soils around mining area and Zn was mainly carried by the Fe-bearing minerals during migration. [ABSTRACT FROM AUTHOR]

Intraplate basalts generally show a geochemical continuum from alkali to tholeiitic basalts. However, the genetic link between these two types of rocks has remained controversial. The Early Jurassic Karamay basalts in the West Junggar terrane, southern Central Asian Orogenic Belt (CAOB), erupted to form a small-volume outcrop in the stable continental intraplate region. The basalts are characterized by aphyric textures without any visible phenocrysts. Thus, they are different from the ubiquitous porphyritic-textured intraplate basalts and have a composition close to that of the mantle-derived primary melt. In contrast to chemically and petrographically well-defined alkali and tholeiitic basalts, the Karamay basalts exhibit transitional compositions spanning from alkali (with normative olivine+nepheline and normative olivine+hypersthene) to tholeiitic (with normative quartz+hypersthene), providing an important case to address the geochemical continuum of intraplate basalts. Similar to the alkali basalts in eastern China, the Karamay basalts have isotopic imprints of sedimentary carbonates, i.e., significantly lighter Mg (δ26Mg = −0.54‰ to −0.34‰) and heavier Zn (δ66Zn = 0.36–0.46‰) isotopes than the normal mantle. However, they display initial ((87Sr/86Sr) t ratios of 0.7047–0.7051, positive ε Nd (t) values (3.3–4.2) and positive anomalies of Nb-Ta-Ti-Zr-Hf, which are not expected in the case of incorporation of recycled carbonates. This contradiction can be reconciled by considering a decarbonation reaction between carbonates (i.e., dolomite and magnesite) and co-existing eclogite in the subducted oceanic slab at pressure >5 GPa, leaving light Mg and heavy Zn isotope signatures in the stagnant eclogite residue in the deep mantle. Combining the geochemical compositions of our samples with the geologic evidence, and considering the previous results of melt-peridotite reaction experiments, we conclude that the Karamay basalts might have originated from the interaction of silica-rich tholeiitic melt derived from the recycled decarbonated eclogite with fertile peridotite during its ascent. Our study highlights that intraplate alkali basalts, especially silica-rich ones (e.g., with SiO 2 >45 wt.%), can be transformed from tholeiitic melts through reaction with peridotite mantle, and demonstrates that deeply recycled oceanic crust stagnated in mantle can serve as a main source for alkaline lavas. Decarbonation reaction between sedimentary carbonates and the silicate oceanic crust during slab subduction may play a vital role in the formation of intraplate basalts characterized by carbonate-imprinted Mg-Zn isotopic compositions and positive anomalies of Nb-Ta-Ti-Zr-Hf. The tholeiitic melts derived from such decarbonated recycled eclogite can evolve to intraplate alkali basalts via reaction with ambient peridotite during ascent. [Display omitted] • Intraplate alkali basalt can form from tholeiitic melt via reaction with peridotite. • Recycled oceanic crust can serve as the main source for alkali basalts. • Low δ26Mg and high δ66Zn of basalts can be inherited from decarbonated eclogite. [ABSTRACT FROM AUTHOR]