Molecular composition and spatial distribution of dissolved organic matter (DOM) in the Pearl River Estuary, China

Environmental context Estuaries play an important role in global carbon cycling in terms of transforming dissolved organic matter (DOM). We describe the molecular composition and spatial distribution of DOM in the Pearl River Estuary, an area severely impacted by anthropogenic activities, and show how DOM composition gradually changes with salinity. The results will help our understanding of the sources and transformations of anthropogenic DOM discharged to the coastal seas. Abstract The Pearl River is the second-largest river in China in terms of water discharge and brings enormous amounts of nutrients and terrestrial organic matter to the South China Sea, which makes the Pearl River Estuary (PRE) highly eutrophic. However, the molecular composition and distribution of dissolved organic matter (DOM) in the PRE have scarcely been investigated. In this study, solid-phase extraction (SPE) was performed to collect DOM samples from PRE along a salinity gradient. The samples were characterised by negative-ion electrospray ionisation (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to analyse their molecular composition and spatial distribution. The FT-ICR MS results showed that the terrestrial organic matter was gradually diluted and/or degraded during the migration from the river to the coastal ocean. Furthermore, both sulfur containing and unsaturated molecules were highly abundant in the upper stream samples, which indicated that anthropogenic input might be another important source of the assigned DOM in PRE. A group of bio-refractory molecules, characterised as carboxylic-rich alicyclic-like molecules, was found to accumulate with the increase of salinity. The composition of the SPE-DOM showed a gradual variation with the salinity and spatial changes; however, the variation was slightly different from those in pristine estuaries. This study demonstrates that the molecular composition of DOM is crucial for elucidating its source and transformation in an estuary.