<p>Black carbon (BC) plays an important role in terrestrial carbon storage and can improve sustainably soil fertility. Nevertheless, the accurate quantification of BC remains a critical issue to fully unravel the functions and dynamics of BC in soil. In this work, we explored the potential of differential scanning calorimetry (DSC) to identify, characterize and quantify charcoal in the soil of pre-industrial charcoal kiln sites (CKS) from a diversity of forest and cropland soils in Belgium and Germany. Pre-industrial charcoals and uncharred soil organic matter (SOM) demonstrated a distinct thermal signature that allowed their discrimination, with charcoal being more thermally stable than SOM. The DSC pattern of charcoals is characterized by one to three specific exotherms varying in size and position depending on soil conditions. From our data, we assume that the thermal moieties within charcoal depend on the strength of chemical bonds of C atoms (increasing with the degree of aromatic condensation and decreasing with weathering) and on the activation energy required to onset the combustion. Despite the specific thermal features of charcoal, its decomposition spans over a wide range of temperatures that overlaps with the thermal signature of uncharred SOM. This stresses the challenge of BC quantification in soil and hinders the use of cut-off temperatures to accurately quantify charcoal in soil. Therefore, charcoal-C content was estimated from the relative height of exotherms attributed either to the combustion of charcoal or SOM. For a selection of 45 soil samples, charcoal-C content estimated by DSC was compared to benzene polycarboxylic acids (BPCA) pattern, a widely used method to quantify BC in soil. The two methods correlated strongly (R<sup>2</sup> = 0.97), with BPCA-C representing about one fifth of DSC-derived charcoal-C. This remind us that operationally-defined BC content has an absolute quantitative value only if the recovery rate is controlled, which is very complicated for many case studies. Overall, our results demonstrate that dynamic thermal analysis is largely under-exploited despite providing rapidly and at low cost quantitatively interpretable information all over the continuum of soil organic matter.</p>