Evaluation of a protocol for the quantification of black carbon in sediments

Formation of highly condensed black carbon (BC) from vegetation fires and wood fuel combustion presumably transfers otherwise rapidly cycling carbon from the atmosphere-biosphere cycle into a much slower cycling geological form. Recently reported BC fractions of total organic carbon (TOC) in surficial marine sediments span a wide range (2-90%), leaving it presently unclear whether this variation reflects natural processes or is largely due to method differences. In order to elucidate the importance of BC to carbon burial the specificity of applied methods needs to be constrained. Here the operating range and applicability of a commonly used chemothermal oxidation (CTO) method is evaluated using putative BC standards, potentially interfering substances, and natural matrix standards. Test results confirm the applicability of the method to marine sediments. Integrity tests with model substrates suggest applicability to low-carbon soils but only with a lower specificity to seawater particulate matter. The BC content of marine sediment samples in a set of studies employing the CTO method proved to be consistent with associated geochemical information. The radiocarbon content of the BC isolate in an environmental matrix standard was shown to be similar to the radiocarbon signature of pyrogenic polycyclic aromatic hydrocarbons (PAHs), here serving as molecular markers of combustion (fraction modern f(M) of BC was 0.065 +/- 0.014 and of PAHS 0.056 +/- 0.020), while being clearly distinct from the radiocarbon content of the bulk TOC (f(M) = 0.61 +/- 0.08). Urgent questions such as the global accumulation rate of black carbon in soils and sediments may prove approachable with the chemothermal oxidation technique of BC quantification.