Isotopic evidence for condensed aromatics from non-pyrogenic sources in soils--implications for current methods for quantifying soil black carbon

Black carbon (BC) is a complex continuum of partly charred organic matter predominantly consisting of condensed aromatic and graphitic moieties and it has high potential for long-term carbon sequestration in soils and sediments. There has been common agreement that BC is exclusively formed by incomplete combustion of organic matter, while non-pyrogenic sources are negligible. In this study, we investigated the stable carbon isotope signature of benzenepolycarboxylic acids (BPCAs) as molecular markers for BC to test if there is also a significant contribution of non-pyrogenic carbon to this fraction in soils. BPCAs were formed by hot nitric acid oxidation of different soils and analyzed by three different procedures: (i) elemental analysis - isotope ratio mass spectrometry (EA-IRMS) of bulk BPCAs and gas chromatography - combustion - isotope ratio mass spectrometry (GC-C-IRMS) of (ii) BPCA trimethylsilyl (TMS) derivatives, and (iii) BPCA methyl derivatives. Best accuracy and precision of isotope measurements were obtained by EA-IRMS of bulk BPCAs although this method has a risk of contamination by non-BC-derived compounds. The accuracy and precision of GC-C-IRMS measurements were superior for methyl derivatives (+/-0.1 per thousand and 0.5 per thousand, respectively) to those for TMS derivatives (+3.5 per thousand and 2.2 per thousand, respectively).Comparison of BPCA delta(13)C values of soil samples prior to and after laboratory and field incubations with both positive and negative (13)C labels at natural and artificial abundances revealed that up to 25% of the isolated BC fraction in soils had been produced in situ, without fire or charring. Commonly applied methods to quantify BC exclusively formed by pyrogenic processes may thus be biased by a significant non-pyrogenic fraction. Further research is encouraged to better define isolated BC fractions and/or understand mechanisms for non-pyrogenic BC production in soils.