Mobility and fractionation of rare earth elements in argillaceous sediments: Implications for dating diagenesis and low-grade metamorphism

Abstract

We report Sm-Nd and Rb-Sr data for the fine fractions of Lower Paleozoic argillaceous rocks from Wales, UK and New York, USA, spanning the range of low-grade metamorphic conditions from the diagenetic zone (zeolite facies) to the epizone (greenschist facies). In all cases, leaching of the fine fractions results in a high 147Sm/144Nd (0.09-0.29) acid-soluble component and a complementary low 147Sm/144Nd (0.05-0.14) residual component. The observed fractionation is an ancient feature related to diagenesis, burial and metamorphism. The magnitude of Sm-Nd fractionation between leachates and residues, as well as the resulting Sm-Nd ages, vary as a function of grain size and metamorphic grade. Uncleaved Welsh mudrocks of the diagenetic zone yield Sm-Nd leachate-residue ages of 453-484 Ma, in agreement with their Llanviian to Caradocian biostratigraphic ages, whereas higher grade rocks of the anchizone and epizone yield Sm-Nd ages as young as 413 Ma. These ages are transitional between the time of deposition and the time of regional deformation related to the Acadian Orogeny at 390 Ma. Distinct convex-upward rare earth element (REE) patterns of the leachates suggest that the precipitation of early diagenetic apatite controls the trace element budget of the rock, forcing a depletion of middle REEs on the subsequently formed diagenetic phyllosilicates. The amount of organic matter present and the extent of later prograde reactions are probable modifiers of this fractionation process. Ordovician and Devonian clastic rocks associated with the Trenton and Onondaga limestones of New York yield single-sample and multi-sample Sm-Nd isochron ages that agree well with their biostratigraphic ages of 454 Ma and 390 Ma, respectively. The REE fractionation observed in shale leachates of the Ordovician Utica Formation is related to Ca/Mg of the bulk rock and hence to the composition of the diagenetic carbonate cement. In all cases the Sm-Nd system remained closed subsequent to the peak of diagenesis or metamorphism, including the North American rocks that show no evidence of being isotopically reset during widespread remagnetization of the subjacent limestone units in the late Paleozoic.