Mass Fractionation Laws, Mass-Independent Effects, and Isotopic Anomalies

Isotopic variations usually follow mass-dependent fractionation, meaning that the relative variations in isotopic ratios scale with the difference in mass of the isotopes involved (e.g., δ 17 O ≈ 0.5×δ 18 O). In detail, however, the mass dependence of isotopic variations is not always the same, and different natural processes can define distinct slopes in three-isotope diagrams. These variations are subtle, but improvements in analytical capabilities now allow precise measurement of these effects and make it possible to draw inferences about the natural processes that caused them (e.g., reaction kinetics versus equilibrium isotope exchange). Some elements, in some sample types, do not conform to the regularities of mass-dependent fractionation. Oxygen and sulfur display a rich phenomenology of mass-independent fractionation, documented in the laboratory, in the rock record, and in the modern atmosphere. Oxygen in meteorites shows isotopic variations that follow a slope-one line (δ 17 O ≈ δ 18 O) whose origin may be associated with CO photodissociation. Sulfur mass-independent fractionation in ancient sediments provides the tightest constraint on the oxygen partial pressure in the Archean and the timing of Earth's surface oxygenation. Heavier elements also show departures from mass fractionation that can be ascribed to exotic effects associated with chemical reactions such as magnetic effects (e.g., Hg) or the nuclear field shift effect (e.g., U or Tl). Some isotopic variations in meteorites and their constituents cannot be related to the terrestrial composition by any known process, including radiogenic, nucleogenic, and cosmogenic effects. Those variations have a nucleosynthetic origin, reflecting the fact that the products of stellar nucleosynthesis were not fully homogenized when the Solar System formed. Those anomalies are found at all scales, from nanometer-sized presolar grains to bulk terrestrial planets. They can be used to learn about stellar nucleosynthesis, mixing in the solar nebula, and genetic relationships between planetary bodies (e.g., the origin of the Moon). They can also confound interpretations based on dating techniques (e.g., 146 Sm- 142 Nd) when they are misidentified as isotopic variations of radiogenic origin. To summarize, there is a world to explore outside of mass-dependent fractionation whose impact is promised to expand as analytical capabilities to measure ever-subtler isotopic anomalies on ever-smaller samples continue to improve.