Redistribution of rare earth elements during diagenesis of turbidite/hemipelagite mudrock sequences of Llandovery age from central Wales

Abstract

Abstract Geochemical studies of recently mapped Upper Llandovery turbidites in central Wales indicate localized rare earth element (REE) mobilization and fractionation in mudrock-dominated sequences. Closely associated turbidite sandstones, turbidite mudstones and laminated anoxic hemipelagites have generally similar major elemental compositions but display strongly differentiated REE distributions. Shale-normalized REE distribution patterns show that anoxic hemipelagites are consistently enriched in the light and middle REE, with greatest enrichment occurring for La-Eu. This enrichment reflects a concentration of millimetre-scale zoned REE-rich monazite nodules in the hemipelagites. In contrast, the REE patterns of the associated turbidites mirror those of the anoxic hemipelagite, being relatively depleted in the light and middle REE, with Nd and Sm generally showing greatest differentiation. The relationship between the concentration of nodules and degree of enrichment of REE in anoxic hemipelagite and turbidite unit thickness imply upward migration of REE into the overlying hemipelagite. However, mass balance considerations suggest that the turbidite-hemipelagite couplets were not necessarily closed systems. Within the turbidites, REE were initially held in unstable volcanogenic minerals and adsorbed on to clay minerals and iron-manganese hydroxides. The REE were liberated into the sediment porewaters during early diagenesis and fractionated in the migrating porewaters as a result of the greater solubility of heavy REE relative to light REE. Expulsion of porewaters from the turbidite sediment during burial carried REE in solution through the intervening hemipelagic layers where REE were precipitated, probably in the presence of organic matter, and possibly initially as the hydrous phosphate rhabdophane which later transformed to monazite. Fractionation of the REE during this process led to preferential enrichment of the light and medium REE within the hemipelagic sediment. The use of REE as indicators of sediment provenance in the Llandovery turbidite-hemipelagite mudrock sequences of central Wales must be treated with caution since significant REE element migration and fractionation is shown to have occurred during their diagenesis. Similar effects might be expected in other sequences comprising interbedded organic-rich/organic-poor mudrock and detailed petrographic analyses should be undertaken to evaluate the possibility of diagenetic REE fractionation and redistribution in conjunction with the use of REE patterns or Sm-Nd isotopes in provenance studies of these rocks.