Diffusion of Sm-Nd in Scheelite and its Significance to Isotopic Dating and Tracing

As the principal ore mineral in various tungsten (-gold) deposits, scheelite (CaWO4) plays an important role in directly dating the timing of ore formation, and in tracing associated material sources through the study of its Sm-Nd geochronology and Nd isotopic characteristics. Since the retention of Sm-Nd systematics within scheelite is presently unconstrained, equivocal interpretations for isotopic data resulting from this method have occurred quite often in previous studies that apply these isotopic data. In order to better elucidate the closure of Sm-Nd in scheelite, the kinetics of Sm and Nd within this mineral lattice were investigated through calculation of diffusion constants presented herein. The following Arrhenius relations were obtained: D-Nd = 4.00exp(-438 kJ center dot mol(-1)/ RT) cm(2)/ s D-Sm = 1.85exp(-427 kJ center dot mol(-1)/ RT) cm(2)/ s showing diffusion rate of Nd is near identical to Sm in scheelite when at the same temperature. However, compared to other rare earth elements (REEs), which have markedly different atomic radii to either Nd or Sm, these are shown to exhibit a great variation in diffusivities. The observed trends in our data are in excellent agreement with the diffusion characteristics of REEs in other tetragonal ABO(4) minerals, indicating that ionic radius is a key constraint to the diffusivity of REEs in the various crystal lattices. With this in mind, the same substitution mechanism and a very slight discrepancy in radii will allow us to infer that significant Sm/Nd diffusional fractionation in scheelite is unlikely to occur during most geological processes. Based upon the diffusion data determined herein, Sm and Nd closure temperatures and retention times in scheelite are discussed in terms of diffusion dynamics. Those results suggest that closure temperatures for Sm-Nd within this mineral are relatively high in contrast to the temperature ranges of ore-formation responsible for scheelite-related deposits, and any later thermal environments. It is likely, therefore, that relevant isotopic information could be easily retained under most geological conditions, since initial crystallization of the scheelite. In addition, comparison of this mineral-element pair over a range of temperatures with some other common minerals used as geochronometers (e.g., zircon and apatite) indicates that Sm-Nd system has a slower diffusive rate in scheelite than for Sr in apatite or Ar in quartz, and only a little faster than for Pb in zircon. It should be noted, within most hydrothermal deposits where zircon has crystallized, its size is typically no more than 100 mu m, whereas scheelite commonly occurs as macroscopic grains. For this reason, the larger dimensions of scheelite would provide a robust Sm-Nd system more able to resist perturbations, relating to any later thermal process. As such Sm-Nd investigations of scheelite are akin to U-Pb within zircon samples used in isotopic dating. These observations indicate that Sm-Nd age and isotopic information can provide reliable data in all but the most extreme case, especially when data are extracted from macroscopic grains of scheelite that are chosen to be "pristine" (i.e., free of surface alteration and/or fractures).