Internal double-spike calibration

Isotopic double spike. The most rigorous approach is to use an isotopic double spike , in which samples are doped with a known quantity of spike Mo which consists of two isotopes in a known ratio (Wetherill 1964 Siebert et al. 2001). These spike isotopes serve as an internal standard to monitor mass fractionation of the sample subsequent to spiking. The fundamental advantage over the element spike is that the spike isotopes follow exactly the same fractionation behavior as the isotopes of interest. A disadvantage is the need to carefully prepare and calibrate the double spike. 

Nonprimed symbols refer to the anal54ical sample prior to extraction, clean-up, etc. Symbols marked with a single prime ( ) refer to the sample extract solution (possibly spiked with internal standard). Symbols marked with a double prime (") refer to a solution of pure analytical standard used for calibration, possibly spiked with an internal standard. Symbols marked with three primes (" ) denote a calibrator prepared by spiking a matrix blank with a known amount of calibration standard, possibly spiked with an internal standard, and taken through the entire analytical procedure. 

The primary disadvantages of the double-spike technique are that (i) the preparation and calibration of a new double spike require significant effort and (ii) four interference-free isotope signals are needed for accurate data reduction, and this also rules out double-spike analysis of elements that feature only two or three isotopes. In many cases, however, these factors will be outweighed by the advantages of the method (i) it offers an instrumental mass bias correction that is similar in application and reliability to internal normalization and hence is even more robust towards matrix effects than external normalization (ii) the approach can correct for laboratory-induced mass fractionation effects, if the spike is added to the samples prior to the chemical processing and (iii) precise elemental concentration data are obtained as a byproduct of the double-spike method. Hence the double-spike method has recently found increasing popularity in MC-ICP-MS stable isotope analysis of non-traditional elements. 

---