Rare earth element geochemistry of Middle Devonian reefal limestones of the Dianqiangui Basin, South China: implications for nutrient sources and expansion of the reef ecosystem

Abstract

The Givetian Age witnessed the greatest expansion of stromatoporoid-coral reefs from low to higher latitudes of the Phanerozoic. Multi-proxy seawater surface temperature reconstruction suggests the establishment of a super-greenhouse climate as a major reason for reef expansion, yet many questions remain. This article presents the results of a rare earth element and yttrium (herein referred to as REY, derived from REE + Y) geochemical study as well as mineralogy and oxygen isotope values of two well-documented Middle Givetian reefal carbonate sections (Jiwozhai and Buzhai) of the Jiwozhai Formation of South China. The nearshore Jiwozhai patch reef succession displays greater biodiversity and more abundant coral than the marginal platform Upper Buzhai reef. Reefal and micritic carbonates of the Jiwozhai section are characterized by shale-like post-Archean Australian Shale (PAAS)-normalized REY patterns, by very weak negative Ce anomaly values (Ce/Ce* 0.80–0.96; average = 0.89), slightly elevated Y/Ho values (28.9–39.1; average = 34.1), and near-unity values of (Pr/Yb)N (average = 0.87), (Pr/Tb)N (average = 0.80), and (Tb/Yb)N (average = 1.09). Moreover, REY patterns of deposits of the Jiwozhai section differ markedly from those of modern seawater. The described geochemical aspects of the Jiwozhai section and the positive correlation of REY and Th contents displayed by the section point to a terrestrial siliciclastic contribution contemporaneous with reef-building. In contrast, REY patterns of the Upper Buzhai reef section samples are similar to those of modern seawater characterized by light rare earth element (LREE) depletion (average (Pr/Yb)N = 0.76), negative Ce anomalies (average Ce/Ce* = 0.88), and average super-chondritic Y/Ho ratios (average = 45.4)). Slightly positive Eu anomalies (Eu/Eu* = 0.93–1.94; average = 1.36) of the Upper Buzhai reef section samples are attributed to the negligible effect of hydrothermal fluids. Middle REE (MREE) enrichment (average (Tb/Yb)N = 1.48) of Buzhai section carbonate samples and positive correlation of REY and Th suggest a riverine input. Combined with siliciclastic mineralogy, oxygen isotope values, and reef-building biota morphology of the studied two sections, we suggest that terrestrial nutrients delivered by rivers far outweighed upwelling as a source of nutrients supplied to the Givetian reef ecosystem of South China. Coral and stromatoporoid in tropic oceans thrived in turbid water containing abundant terrestrial sediment and the nutrient-laden water helped expand reef-builder habitats during the Givetian time.