The role of phosphates for the Lu?Hf chronology of meteorites

The 176Lu–176Hf isotopic system is widely used for dating and tracing cosmochemical and geological processes, but still suffers from two uncertainties. First, Lu–Hf isochrons for some early Solar System materials have excess slope of unknown origin that should not be expected for meteorites with ages precisely determined with other isotopic chronometers. This observation translates to an apparent Lu decay constant higher than the one calculated by comparing ages obtained with various dating methods on terrestrial samples. Second, unlike the well constrained Sm/Nd value (to within 2%) for the chondritic uniform reservoir (CHUR), the Lu/Hf ratios in chondrites vary up to 18% when considering all chondrites, adding uncertainty to the Lu/Hf CHUR value. In order to better understand the Lu–Hf systematics of chondrites, we analyzed mineral fractions from the Richardton H5 chondrite to construct an internal Lu–Hf isochron, and set up a numerical model to investigate the effect of preferential diffusion of Lu compared to Hf from phosphate, the phase with the highest Lu–Hf ratio in chondrites, to other minerals. The isochron yields an age of 4647±210 million years (Myr) using the accepted 176Lu decay constant of 1.867±0.008×10−11yr−1. Combining this study with the phosphate fractions measured in a previous study yields a slope of 0.08855±0.00072, translating to a 176Lu decay constant of 1.862±0.016×10−11yr−1 using the Pb–Pb age previously obtained, in agreement with the accepted value. The large variation of the Lu/Hf phosphates combined with observations in the present study identify phosphates as the key in perturbing Lu–Hf dating and generating the isochron slope discrepancy. This is critical as apatite has substantially higher diffusion rates of rare earth elements than most silicate minerals that comprise stony meteorites. Results of numerical modeling depending of temperature peak, size of the grains and duration of the metamorphic event, show that diffusion processes in phosphate can produce an apparently older Lu–Hf isochron, while this effect will remain negligible in perturbing the Sm–Nd chronology. Our results suggest that only type 3 chondrites with the lowest metamorphic grade and large minerals with minimal diffusive effects are suitable for determination of the Lu–Hf CHUR values and the Lu decay constant respectivel