Fractionation and mixing in a thermal ionization mass spectrometer source: Implications and limitations for high-precision Nd isotope analyses

Abstract

We present a large dataset of normal Nd standard analyses to evaluate the adequacy of commonly used “laws” to correct for the mass dependent isotope fractionation introduced in a thermal ionization mass spectrometer (TIMS) source, and to assess if the assumption of homogenous sample evaporation and ionization from one sample domain on the filament can be considered valid when obtaining high precision (better than 5 ppm, 2 σ) 142Nd/ 144Nd ratios for studies in geo- and cosmochemistry. The exponential law is fully adequate to correct for the mass fractionation at the current level of obtainable precision and surprisingly performs better than the Rayleigh law. Our modelling shows that the observed correlations in the isotope ratios that remain after data have been corrected using the exponential law are a consequence of correlated uncertainties in counting statistics. These correlations are therefore not from residuals resulting from inadequate correction. Application of the exponential law, however, assumes evaporation from a single homogenous domain on the filament—a condition which was impossible to maintain even under optimal sample loading and heating conditions. While a majority of samples showed an increase in heavy/light isotope ratio with time (normal fractionation), many samples showed the reverse trend (reverse fractionation) indicating evaporation and mixing from variably depleted domains on the filament. Our modelling suggests that up to 50% of the calculated external reproducibility (=standard deviation of the population, σ p of n independent measurements) can be explained by the ion emission from multiple domains of somewhat different isotopic composition on the filament. The fractionation behaviour of a sample is not necessarily a good indicator of the extent of domain mixing as mixing effects in data collected during reverse fractionation are similar to those of data collected during normal fractionation before and after periods of reverse fractionation. Domain mixing effects in 142Nd/ 144Nd isotope ratios can be assessed by examining variations in stable 148Nd/ 144Nd and 150Nd/ 144Nd ratios. The 148Nd and 150Nd data from recent reports of 142Nd deficits in terrestrial samples suggest that the 142Nd anomalies are likely produced from domain mixing during analysis rather than from the decay of short-lived 146Sm during the early history of the earth. It is imperative to measure all the isotopes of Nd to the utmost possible precision and to examine domain mixing effects by normalizing the data using multiple isotope pairs.