Abstract

This chapter is devoted to the analytical methods employed for making high precision isotope ratio measurements that preserve naturally occurring mass-dependent isotopic variations. The biggest challenge in making these types of measurements is deconvolving mass-dependent isotopic fractionation produced in the laboratory and mass spectrometer, from naturally occurring mass-dependent isotopic fractionation, because the patterns of isotope variation produced by these processes are identical. Therefore, the main theme of this chapter is the description and mathematical treatment of mass-dependent isotopic variations and the possible pitfalls in deconvolving instrumental mass bias from naturally occurring mass-dependent isotopic variations. This chapter will not attempt to catalog methods for isotopic analysis of different elements. These details are better discussed in later chapters where ‘element specific’ analytical issues are covered. Rather, the effort in the chapter will be to focus on those specific items that make mass analysis of non-traditional isotopes challenging and unique, and the methods that can be employed to make precise and accurate isotope ratios. Isotopic analysis of non-traditional isotopes is made using three main types of mass spectrometers. Elements that can easily be introduced as gases, such as Cl or Br, are typically analyzed using a gas source mass spectrometer. In contrast, metal elements are analyzed using either a thermalionization mass spectrometer (TIMS) or a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). The main difference between these three types of instruments is how the sample is introduced into the instrument, and how the sample is ionized. In contrast, the analyzer part of each instrument is similar. All three types of instruments use a stack of lenses with variable potential to focus the ion beam, a magnet to resolve the ion beam into different masses, and a series of collectors to measure ion currents of different isotopes simultaneously. The core of the mass analyzer …

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