Use of carbon isotopic ratios in nontargeted analysis to screen for anthropogenic compounds in complex environmental...

Analytical data for ultra-high-performance liquid chromatography (UHPLC), nontargeted, high-resolution, mass-spectrometry (HR/MS) molecular features from a wide array of samples are used to calculate ¹³C₁¹²C_(n-1)/¹²C_n isotopologue ratios. These ratios increase with molecular carbon number roughly following a trend defined by atmospheric carbon. When the effective source reservoir ¹³C/¹²C ratio is calculated from the isotopologue ratio (assuming a fractionation factor of unity), features in biotic samples uniformly are tightly grouped, proximate to atmospheric ¹³C/¹²C ratio. In contrast, features in soil natural organic matter (NOM), dust NOM and anthropogenic compounds range from proximate to relatively divergent from atmospheric ¹³C/¹²C. For the NOM, ¹³C/¹²C ratios are consistent with an expected preferential volatilization of ¹²C, rendering features in soil NOM ¹³C-enriched and some features in dust NOM ¹³C-depleted. Anthropogenic compounds tend to diverge most dramatically from atmospheric ¹³C/¹²C, generally toward ¹³C-depletion, but pesticides we tested tended toward ¹³C-enriched. This pattern is robust and evident in: i) anthropogenic vs natural features in dust; ii) perfluorinated compounds in standards and as soil contaminants; and iii) sunscreen compounds in commercial products and wastewater. Considering the observed wide ¹³C/¹²C range for anthropogenic compounds, we suggest Rayleigh distillation during synthetic processes commonly favors one isotope over the other, rendering a source reservoir that is progressively depleted as synthesis proceeds and, consequently, generates a wide variation in ¹³C/¹²C for man-made products. However, kinetic-isotopic effects and/or synthesis from petroleum/natural gas might contribute to the anthropogenic isotopic signature as well. Regardless of cause, ¹³C/¹²C can be used to cull HR/MS molecular features that are more likely to be of anthropogenic or non-biotic origin.