Apatite-glaucony association in the Ediacaran Doushantuo Formation, South China and implications for marine redox conditions

Abstract Major phosphogenic events took place in the late Paleoproterozoic and the Ediacaran, both of which followed an episode of atmospheric oxygenation. These apparent coincidences have led to suggestions that the Precambrian phosphorus cycle was partly regulated by oceanic redox conditions, although direct evidence is lacking. In this paper, we report the discovery of glaucony in drill cores from the phosphorite-rich Ediacaran Doushantuo Formation at Weng'an, South China, which provides new insights into redox conditions and geochemical cycles during the deposition and early diagenesis of the lower Doushantuo Formation. The presence of flaser and lenticular bedding in the sandstones suggests deposition in a tidally-influenced shallow water environment. Apatite is present as millimeter-scale flasers in sandstones, but more commonly as intraclastic grains. Glaucony typically occurs as interstitial aggregates cementing and replacing detrital minerals and phosphatic grains, with an upsection decrease in abundance. The Doushantuo glauconies have consistently high K2O (7.6 – 9.6 wt%). In particular, phosphorite-hosted glaucony has generally higher total iron (TFe2O3) than sandstone-hosted glaucony, consistent with Al3+ - Fe3+ substitution in the octahedral site, as supported by Raman peaks slightly shifted towards lower wavenumbers for higher Fe content. A decrease in detrital input probably resulted in limited Al availability during early diagenesis, which in turn led to the waning of glaucony upsection. The phosphate grains do not show any negative Ce anomalies, consistent with precipitation of authigenic apatite in suboxic environments with insignificant preferential remobilisation of Ce during deposition and early diagenesis. REE + Y features show variable diagenetic REE enrichment in phosphorites, but identical concave-down patterns. The wide occurrence of glaucony cement further documents the presence of a generally suboxic early diagenetic environment on the seafloor, which was in active exchange with bottom seawater. Slight fluctuations of redox states in the porewater and bottom water would have promoted the cycling of Fe, enrichment of phosphate and REE, and extensive glaucony authigenesis. Therefore, the glaucony-bearing phosphorites in the Doushantuo Formation are a direct result of Fe-redox driven diagenesis. Apatite-glaucony association likely forms in suboxic environments and is considered as a useful mineralogical proxy for paleoredox conditions on the Precambrian ocean floors.