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 delta Cu-65 ( + 0.14 +/- 0.09 parts per thousand, 1 sigma) but heavy delta Zn-66 (0.51 +/- 0.11 parts per thousand, 1 sigma). The elevated delta Zn-66 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 delta Cu-65 range from -6.42 parts per thousand to +19.73 parts per thousand and a modest delta Zn-66 range of +025 parts per thousand to +0.78 parts per thousand. 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, delta Zn-66 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 parts per thousand). 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. (C) 2016 Elsevier B.V. All rights reserved.

Publication name	CHEMICAL GEOLOGY, 445 24-35; 10.1016/j.chemgeo.2016.01.016 DEC 16 2016
Author(s)	Lv, Yiwen; Liu, Sheng-Ao; Zhu, Jian-Ming; Li, Shuguang
Corresponding author	LIU Shengao   lsa@cugb.edu.cn   China Univ Geosci, 29 Xueyuan Rd, Beijing 100083, Peoples R China.
Author(s) from IGCAS	ZHU Jianming

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