Benzenepoly(carboxylic acid)s as Exclusive Intrinsic Markers to Assess Riverine Export of Dissolved Black Carbon

Landscape fires annually generate large quantities of black carbon. The water-soluble fraction of black carbon (i.e., dissolved black carbon/DBC) is an important constituent of the dissolved organic carbon (DOC) pool, playing a crucial role in the global budget of refractory carbon and climate change. A key challenge in constraining the flux and fate of riverine DBC is to develop targeted and accurate quantification methods. Herein, we report that benzenepentacarboxylic acid (B5CA) intrinsically present in DBC can be used as an exclusive and holistic marker (representing both condensed aromatics and less-/nonaromatic fractions) for DBC quantification. B5CA was universally detected in water extractions of biochar and fire-affected soils with relatively large abundance but not produced by nonthermogenic processes. It has good mobility in the environment as it is not readily precipitated by cations or adsorbed by common geosorbents. B5CA also represents the recalcitrant components of DBC with excellent stability against photodegradation and biodegradation. Applying B5CA as the DBC marker in surface waters of the Changjiang River (i.e., the third largest river in the world), we calculate the DBC concentration in the downstream Changjiang River to be 4.8 +/- 5.5% of the DOC flux. Our work provides a simple and reliable approach for the accurate quantification and source tracking of DBC in the soil and aquatic carbon pools.