Mineralogic controls on REE mobility during black-shale diagenesis

Abstract The Llandeilo-Caradoc black shales of southwest Wales, U.K. record a paragenetic sequence that requires redistribution of rare earth elements (REE) on a mineralogic scale during diagenesis. The main evidence for this redistribution is formation and replacement of REE-rich apatite and monazite and variations in whole-rock REE patterns. The processes that produce these mineralogic changes create a diagenetic overprint on the Llandeilo-Caradoc black shales that obscures geochemical information related to both provenance and paleoenvironmental conditions of deposition. Periods of open-system conditions existed during the diagenetic alteration of the Llandeilo-Caradoc black shales, which allow an evaluation of the extent and timing of the REE redistribution inferred from petrography. The observed variations in La/Sm ratios in the whole-rock REE patterns are strong evidence that REE were redistributed on a scale greater than an individual hand sample. This change in the whole-rock REE pattern altered the Cerium anomaly by as much as 20% and produced a range in the Sm/Nd ratio from 0.14 to 0.20. This change in the whole-rock Sm/Nd ratio indicates a disturbance in the Sm-Nd isotopic system at about 460 Ma that can be directly linked to the formation and dissolution of diagenetic apatite and monazite during diagenesis. One effect of this disturbance is to alter the range in Nd model age for the Llandeilo-Caradoc black shales from 1.6 to 1.8 Ga to about 1.4 to 2.25 Ga, thus complicating any interpretation of provenance. The ability to link petrographic observations from a black shale to measurable whole-rock geochemical changes provides us with one tool to evaluate the presence of a diagenetic overprint on trace elements commonly used in paleoenvironmental reconstruction.