Rare earth elements as a tool for studying the formation of cemented layers in an area affected by acid mine drainage

In a profile with two cemented layers sampled in an area affected by acid mine drainage, both have rare earth element (REE) signatures with positive Ce anomalies in the Post Archean Australian Shale-normalised patterns. Both cemented layers have higher contents of environmentally relevant metals (Cd, Co, Cu, Fe, Mn, U, and Zn) than the over- and underlying unconsolidated Quaternary sediments and are depleted of Al, Ca, K, and Mg. The cemented layers are enriched in middle and heavy REE, but only the bulk pattern of the lower cemented layer reveals a positive Ce anomaly. For the upper cemented layer, this positive Ce anomaly was only determined by spatially resolved laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) studies only for segments with a high abundance of Mn, occurring as Mn phases as proven by energy dispersive X-ray spectroscopy. The Mn phases are formed secondarily to the ferric cement and are especially enriched in Ce and Co. The Ce anomaly of the lower cemented layer most probably is inherited from groundwater to the ferric cement, whereas the Ce anomaly of the upper cemented layer is the result of preferential scavenging of Ce onto the Mn phases compared to other REE.