Chemodiversity of water-extractable organic matter in sediment columns of a polluted urban river in South China

Highlights: • Sediment WEOM increased from upstream to downstream due to increased urban inputs. • High load of less-degraded S-containing surfactants accumulated in sediment WEOM. • Greater alteration in WEOM occurred in surface (down to 40 cm) than in deep sediment. • WEOM varied little with depth at river mouth due to intensive water exchange. Dissolved organic matter (DOM) in sediments of polluted rivers significantly contributes to oxygen consumption and river blackening and odorization. However, the chemodiversity of DOM at different depths or river reaches is poorly known. Here, we studied the storage and molecular-level signatures of water-extractable organic matter (WEOM) in the sediment column (0–100 cm) of the upper, middle, and lower mainstream of Maozhou River (a polluted river in Shenzhen, China, with 40 years of urbanization) using optical spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry. The sediment WEOM level increased from upstream to downstream. The relative abundances of sulfur-containing surfactants in all sediment WEOM were higher than those previously reported for surface water DOM. The WEOM in surface sediment had higher aromaticity, molecular size, and nominal oxidation state of carbon and greater signals from anthropogenic inputs than did deep sediment at the upper and middle mainstream sites. However, these characteristics varied little between surface and deep sediments at the lower mainstream site, probably due to intensive surface water and pore water interactions. The sediment WEOM at 0–40 cm in the middle mainstream showed a greater anthropogenic signature (e.g., more surfactant and dissolved black carbon contributions) than any other sediment. We demonstrate strong anthropogenic impacts on the surface sediment over decades of urbanization.