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

ABSTRACT: 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.

SUBMITTER: Washington JW

PROVIDER: S-EPMC8287460 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Carbon nanotube (CNT) production is rapidly growing, and there is a need for robust analytical methods to quantify CNTs at environmentally relevant concentrations in complex organic matrices. Because physical and thermal properties vary among different types of CNTs, we studied 14 single-walled (SWCNTs) and multiwalled CNTs (MWCNTs). Our aim was to apply a classic analytical air pollution method for separating organic (OC) and elemental carbon (EC) (thermal optical transmittance/reflectance, TOT/R) to environmental and biological matrices and CNTs. The TOT/R method required significant modification for this analysis, which required a better understanding of the thermal properties of CNTs. An evaluation of the thermal properties of CNTs revealed two classes that could be differentiated using Raman spectroscopy: thermally "weak" and "strong." Using the programmed thermal analysis (PTA) method, we optimized temperature programs and instituted a set of rules for defining the separation of OC and EC to quantify a broad range of CNTs. The combined Raman/PTA method was demonstrated using two environmentally relevant matrices (cyanobacteria (CB) and urban air). Thermal evaluation of CB revealed it to be a complex matrix with interference occurring for both weak and strong CNTs, and thus a pretreatment method was necessary. Strong CNT masses of 0.51, 2.7, and 11 μg, corresponding to concentrations of 10, 54, and 220 μg CNT/g CB, yielded recoveries of 160 ± 29%, 99 ± 1.9%, and 96 ± 3.0%, respectively. Urban air was also a complex matrix and contained a significant amount (12%) of background EC that interfered greatly with weak CNTs and minimally with strong CNTs. The current detection limit at 99% confidence for urban air samples and strong CNTs is 55 ng/m(3) (0.33 μg). Overall, the PTA method presented here provides an initial approach for quantifying a wide range of CNTs, and we identify specific future research needs to eliminate potential interferences and lower detection limits.

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

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