Germanium/silica ratios in diagenetic chert nodules from the Ediacaran Doushantuo Formation, South China

Germanium/silica (Ge/Si) ratios of dolostone- and mudstone-hosted chert nodules from the Ediacaran (635–542 Ma) Doushantuo Formation in the Yangtze Gorges area, South China, are reported. These chert nodules typically have a calcite rim, a pyrite rim, and a silica core, the latter sometimes containing disseminated pyrite. The silica core was precipitated by early diagenetic replacement of carbonate and silty/muddy sediments. Two types of chert nodules are identified based on their mineralogy and geochemistry. Type-1 chert nodules are poor in disseminated pyrite in the silica core. They also have low Al, and show a strong positive correlation between Al contents and Ge/Si with a near-zero or negative intercept. In contrast, Type-2 chert nodules contain abundant disseminated pyrite in the silica core and show a weakly positive correlation between Ge/Si ratios and Al contents (with a large positive intercept on the Ge/Si axis). The Ge/Si of Doushantuo nodules are greater than those of Cretaceous deep-sea cherts, suggesting that the Ge/Si ratio of Ediacaran seawater/porewater was greater than the Cretaceous due to the more effective discrimination against Ge by inorganic opal precipitation relative to biogenic opal precipitation. The positive correlation between Ge/Si and Al can be interpreted using a mixing model with a pure chert (characterized by a low Ge/Si ratio) and an Al-rich endmember (characterized by a high Ge/Si ratio). The latter is most likely represented by a clay component, but the model-based estimate of the Ge/Si ratio inferred for the Al-rich (clay) endmember is much higher than that of Phanerozoic clay minerals. These high Ge/Si ratios for the clay endmember may be related to the generally high Ge/Si ratio of Ediacaran seawater, but could also be related to clay–organic matter interactions. Organic matter absorbed to clays could provide an additional source of Ge because certain organic molecules are known to have a high affinity for Ge due to their strong metal ion-chelating properties. The high Ge/Si ratio of the Al-rich endmember in Type-1 chert nodules suggests that Ge in porewaters from which these cherts precipitated may have been dominated by Ge–organic complexes. The low Ge/Si ratio inferred for the Al-rich endmember in Type-2 chert nodules is therefore taken to indicate that Ge was released from organic matter, perhaps due to anaerobic degradation of organic matter (accompanied by the formation of pyrite), and was redistributed between clay–organic endmembers and pure chert, resulting in a non-zero intercept in the Ge/Si vs. Al2O3 plots. These observations suggest that a strong terrestrial influence in a restricted sedimentary basin or a high content of dissolved organic carbon in Ediacaran seawater and porewater may have contributed to the dominance of Ge–organic complexes in the Doushantuo basin in the Yangtze Gorges area.

Research Highlights
► Ge/Si of Ediacaran Doushantuo chert nodules are measured by Laser-ablation ICP-MS.
► Chert nodule Ge/Si is related to Al content and formation of disseminated pyrites.
► Ge in the Doushantuo porewater is in the form of Ge-organic-clay complex.
► Chelating of Ge by organic compounds suggests high DOC content in porewater.