Evaluating chlorine isotope effects from isotope ratios and mass spectra of polychlorinated molecules

Compound-specific chlorine isotope analysis receives much interest to assess the fate of chlorinated hydrocarbons in contaminated environments. This paper provides a theoretical basis to calculate isotope ratios and quantify isotope fractionation from ion-current ratios of molecular- and fragment-ion multiplets. Because both Cl-35 and Cl-37 are of high abundance, polychlorinated hydrocarbons consist of molecules containing different numbers of Cl-37 denoted as isotopologues. We show that, during reactions, the changes in isotopologue ratios are proportional to changes in the isotope ratio assuming a nonselective isotope distribution in the initial compound. This proportionality extents even to fragments formed in the ion source of a mass spectrometer such as C2Cl2 (double dechlorinated fragment of perchloroethylene, PCE). Fractionation factors and kinetic isotope effects (KIE) may, therefore, be evaluated from isotope, isotopologue or even fragment ratios according to conventional simple equations. The proportionality is exact with symmetric molecules such as dichloroethylene (DCE) and PCE, whereas it is approximately true with molecules containing non-reactive positions such as trichloroethylene (TCE). If in the latter case isotope ratios are derived from dechlorinated fragments, e.g., C2HCl2, it is important that fragmentation in the ion source affect all molecular positions alike, as otherwise isotopic changes in reactive positions may be underrepresented.