Enrichment of geogenic phosphorus in a coastal groundwater system: New insights from dissolved organic matter characterization.

High concentrations of geogenic phosphorus (P) in coastal aquifer systems pose a serious and continuous threat to the health of marine ecosystems. A major source for geogenic P enrichment in aquifer systems is the mineralization of P-containing organic matter. However, the mechanisms that drive the enrichment remain unclear. Therefore, our study sought to characterize the occurrence, sources, and enrichment mechanisms of geogenic P in a coastal confined aquifer system of the Pearl River Delta, southern China. To achieve this, we conducted Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and fluorescence excitation-emission-matrix spectra (EEMs) as well as hydrochemistry and stable carbon isotope analyses. Our findings indicated that intense degradation of P-containing organic matter produced up to 8.07 mg/L of geogenic P in a reducing environment with abundant organic matter. The dissolved organic matter (DOM) of high-P groundwater (P > 1 mg/L) contained more humic-like fluorophores and exhibited higher humification. Groundwater with high P concentrations contained more aliphatic compounds and highly unsaturated-low O compounds, and the enrichment of P was mostly associated with CHOP compounds in the region of aliphatic compounds and CHON2P compounds in the region of highly unsaturated-low O compounds. Different types of dissolved organic phosphorus (DOP) can be mineralized into P, and even the mineralization of phosphonates takes precedence over the more unstable phosphate esters. P produced by the metabolism of different types of DOP was assimilated by marine microorganisms (e.g., heterotrophic bacteria and archaea), and the newly synthesized organic P compounds by chemosynthesis were subsequently released into the groundwater. Over time, P continues to be enriched in the aquifer system. This study provides new insights into subsurface P cycling in coastal aquatic systems.