Bacteria, guano and soot: Source assessment of organic matter preserved in black laminae in stalagmites from caves of the Sierra de Atapuerca (N Spain)

Speleothems are a recognized source of paleoclimatic information, but their value as a source of signals from human activities in caves with an archaeological record has rarely been explored. Previous studies of speleothems in the Sierra de Atapuerca karst system (Burgos, northern Spain) revealed an important human fossil record, provided information about human activities in and around these caves, and the impacts on their natural environment. The present study reports the results of molecular characterization of dark-colored laminae from the stalagmites Ilargi (Galería de las Estatuas) and GS1, GS2, and GS3 (Galería del Silo), by pyrolysis-GC-MS (Py-GC-MS) and thermally assisted hydrolysis and methylation (THM-GC-MS). The features of the organic matter demonstrate the presence of (1) a dominant aliphatic fraction probably from in situ bacterial and ex situ plant-derived lipids, (2) black carbon (from soot and/or charcoal), (3) polysaccharides and N-rich moieties (probably from bat guano and microbial sources), and (4) a signal of terpenoid derivatives that may originate from the overlying limestone (kerogen) and extant gymnosperm resin (soils) or cyanobacteria (cave). Some plant-derived lignin may be present as well but was not identified unambiguously. It is concluded that this approach allows identifying multiple general sources of organic matter which can help understand speleothem formation processes, and evidence of soot deposition could be clearly linked to human activities