Rare earth elements in Holocene reefal microbialites: a new shallow seawater proxy

Abstract

The concentration of rare earth elements and yttrium (REE + Y) was determined in Holocene Mg-calcite microbialites from shallow reef framework cavities at Heron Reef, Great Barrier Reef. Shale-normalized REE + Y patterns of 52 microbialite samples show: (1) uniform heavy REE enrichment (Nd SN/Yb SN = 0.236, SD = 0.026); (2) consistent negative Ce and positive La anomalies; (3) marine Y/Ho ratios (56.17, SD = 2.66); and (4) slightly positive Gd anomalies. All of these features are consistent with the geochemistry of well-oxygenated, shallow ambient seawater. REE partition coefficients were calculated relative to shallow Coral Sea seawater. They are uniform (relative SD = 10.2%) across the entire mass range and almost two orders of magnitude higher than those between coral and seawater. Hence, terrigenous detritus-free, modern microbialites are a more reliable proxy for seawater REE chemistry than are skeletal carbonates. Ancient limestones have been considered largely problematic as sources for REE proxies owing to perceived problems with diagenesis, partly on the basis of relatively high REE concentrations in some limestones compared to modern skeletal carbonates. However, high REE concentrations in modern microbialites suggest that ancient limestones with relatively high REE concentrations, if not contaminated by terrigenous detritus, may reflect original seawater chemistry. Terrigenous contamination, if present, is readily detectable on the basis of co-occurring trace element concentrations (Sc, Hf, Th) and Y/Ho ratio. Hence, ancient, particularly reefal, limestones may provide reliable seawater REE proxies. The occurrence of microbialites in clean limestones as old as 3.5 Ga suggests the possibility of reconstructing shallow marine REE chemistry over most of Earth history with important implications for paleogeography and paleoredox studies.