Refractory organic matter in sediments from the North–West African upwelling system: abundance, chemical structure and origin

Refractory (insoluble and nonhydrolyzable) organic matter (ROM) was studied in sediments underlying the north–west African upwelling system. Two core samples: beginning of glacial isotope stage 4 (ca. 70,000 yr BP; depth bsf 360 cm) and interglacial isotope substage 5d (ca. 90,000 yr BP; depth bsf 480 cm) were analyzed, along with a surface sample. ROM, which accounts for a substantial part of the total organic matter (OM) in these sediments (ca. 20% for the two core samples and 10% for the surface sample), was isolated and examined for its morphological and chemical features using a combination of transmission and scanning electron microscopy, spectroscopy (FTIR, solid state 13C NMR) and analytical pyrolysis (Curie point flash pyrolysis–GC–MS). These studies allowed the chemical structure of the three ROMs (chiefly based on melanoidin-type macromolecules) and their mechanism of formation (degradation–recondensation of products mainly derived from proteinaceous material) to be established. Such a formation probably began in the water column and continued within the sediment upper layers. Important differences, concerned both with OM chemical structure and preservation mechanism, were noted upon comparison with recently studied sediments underlying the Peru upwelling system. These differences between the two systems, in spite of similarities in primary production, must reflect the combined influence of factors such as upwelling intensity (primary productivity), water depth and iron supply.