Revealing degradation pathways of soluble and dissolved organic matter in alluvial-lacustrine aquifer systems impacted by high levels of geogenic ammonium

Abstract

The excessive presence of geogenic ammonium (NH₄⁺) in groundwater poses a global environmental concern, commonly linked to the degradation of nitrogen-containing dissolved organic matter (DOM). However, there is a gap in systematic studies on the combination of soluble organic matter (SOM) in sediments and DOM in groundwater, with few indoor incubation experiments to validate their degradation pathways. This study utilized ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to analyze the molecular characteristics of DOM and SOM in aquifer systems affected by geogenic NH₄⁺. Subsequently, indoor incubation experiments spanning up to 140 d were conducted to verify the degradation pathways. The experimental results revealed a two-phase degradation process for both the DOM and SOM. The initial stage was characterized by the degradation of aliphatic compounds (ALC) with the production of polyphenols (PPE) and highly unsaturated compounds (HUC). The second stage was dominated by the degradation of PPE and HUC, accompanied by the re-consumption of some ALC, while more recalcitrant HUC persisted. Notably, the first stage of SOM degradation exceeded that of DOM degradation, indicating that SOM exhibited greater resistance to aging. This phenomenon may be attributed to a wider range of active enzymes in sediments, the rapid replenishment of SOM by organic matter in sediments, or the accelerated degradation of DOM. The experimental results aligned with the molecular characterization of DOM and SOM in actual aquifer systems. It is hypothesized that NH₄⁺ produced through the direct mineralization of SOM may contribute more to the enrichment of NH₄⁺ in groundwater than that produced through the mineralization of DOM. This study is the first to analyze DOM and SOM together in aquifer systems and validate their degradation pathways through incubation experiments, thereby providing novel insights into the enrichment of geogenic NH₄⁺ in groundwater.