Investigating Rare Earth Element Systematics in the Marcellus Shale

Abstract:

The lanthanide series of elements (the 14 rare earth elements, REEs) have similar chemical properties and respond to different chemical and physical processes in the natural environment by developing unique patterns in their concentration distribution when normalized to an average shale REE content. The interpretation of the REE content in a gas-bearing black shale deposited in a marine environment must therefore take into account the paleoredox conditions of deposition as well as any diagenetic remobilization and authigenic mineral formation. We analyzed 15 samples from a core of the Marcellus Shale (Whipkey ST1, Greene Co., PA) for REEs, TOC, gas-producing potential, trace metal content, and carbon isotopes of organic matter in order to determine the REE systematics of a black shale currently undergoing shale gas development. We also conducted a series of sequential leaching experiments targeting the phosphatic fractions in order to evaluate the dominant host phase of REEs in a black shale. Knowledge of the REE system in the Marcellus black shale will allow us to evaluate potential REE release and behavior during hydraulic fracturing operations. Total REE content of the Whipkey ST1 core ranged from 65-185 μg/g and we observed three distinct REE shale-normalized patterns: middle-REE enrichment (MREE/MREE* ~2) with heavy-REE enrichment (HREE/LREE ~1.8-2), flat patterns, and a linear enrichment towards the heavy-REE (HREE/LREE ~1.5-2.5). The MREE enrichment occurred in the high carbonate samples of the Stafford Member overlying the Marcellus Formation. The HREE enrichment occurred in the Union Springs Member of the Marcellus Formation, corresponding to a high TOC peak (TOC ~4.6-6.2 wt%) and moderate carbonate levels (CaCO₃ ~4-53 wt%). Results from the sequential leaching experiments suggest that the dominant host of the REEs is the organic fraction of the black shale and that the detrital and authigenic fractions have characteristic MREE enrichments. We present our conclusions on the impact of depositional setting and diagenetic remobilization and authigenic mineral formation on the REE system in the Marcellus Shale.