Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography–isotope‐ratio mass spectrometry of benzene polycarboxylic acids

Abstract

Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well-established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound-specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post-analysis correction for the accurate measurement of δ¹³C values, leading to increased measurement error. Here, we describe a method for δ¹³C isotope ratio measurement and quantification of BPCAs from soil-derived PyOM, based on ion-exchange chromatography (IEC-IRMS). The reproducibility of the δ¹³C measurement of individual BPCAs by IEC-IRMS was better than 0.35‰ (1σ). The δ¹³C-BPCA analysis of PyOM in soils, including at natural and artificially enriched ¹³C-abundance, produced accurate and precise δ¹³C measurements. Analysis of samples that differed in δ¹³C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual δ¹³C-BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of δ¹³C-BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways.