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Isotope fractionation occurs during a phase transition, when the ratio of light to heavy isotopes in the involved molecules changes. When water vapor condenses (an equilibrium fractionation), the heavier water isotopes (18 O and 2 H) become enriched in the liquid phase while the lighter isotopes (16 O and 1 H) tend toward the vapor phase. [1]
Equilibrium isotope fractionation is the partial separation of isotopes between two or more substances in chemical equilibrium. Equilibrium fractionation is strongest at low temperatures, and (along with kinetic isotope effects) forms the basis of the most widely used isotopic paleothermometers (or climate proxies): D/H and 18 O/ 16 O records from ice cores, and 18 O/ 16 O records from calcium ...
The equations can be used to describe an isotope fractionation process if: (1) material is continuously removed from a mixed system containing molecules of two or more isotopic species (e.g., water with 18 O and 16 O, or sulfate with 34 S and 32 S), (2) the fractionation accompanying the removal process at any instance is described by the ...
The difference is whether the relative abundance is with respect to all the nitrogen, i.e. 14 N plus 15 N, or just to 14 N. Since the atmosphere is 99.6337% 14 N and 0.3663% 15 N, a is 0.003663 in the former case and 0.003663/0.996337 = 0.003676 in the latter.
Denitrification can lead to a condition called isotopic fractionation in the soil environment. The two stable isotopes of nitrogen, 14 N and 15 N are both found in the sediment profiles. The lighter isotope of nitrogen, 14 N, is preferred during denitrification, leaving the heavier nitrogen isotope, 15 N, in the residual matter.
Since its original descriptions, the Urey–Bigeleisen–Mayer equation has taken many forms. Given an isotopic exchange reaction + = +, such that designates a molecule containing an isotope of interest, the equation can be expressed by relating the equilibrium constant, , to the product of partition function ratios, namely the translational, rotational, vibrational, and sometimes electronic ...
Transient kinetic isotope effects (or fractionation) occur when the reaction leading to isotope fractionation does not follow pure first-order kinetics (FOK) and therefore isotopic effects cannot be described with the classical equilibrium fractionation equations or with steady-state kinetic fractionation equations (also known as the Rayleigh equation). [1]
The δ values and absolute isotope ratios of common reference materials are summarized in Table 1 and described in more detail below. Alternative values for the absolute isotopic ratios of reference materials, differing only modestly from those in Table 1, are presented in Table 2.5 of Sharp (2007) [1] (a text freely available online), as well as Table 1 of the 1993 IAEA report on isotopic ...