Marine Recalcitrant Dissolved Organic Matter Gained by Processing at Sandy Subterranean Estuaries

The sandy subterranean estuary (STE) connecting fresh groundwater to saline sea water is characterized by strong geochemical (salinity, redox, and pH) gradients, with evidence emerging for its role as a hot spot for consumption of labile substrates. This inspired us to conduct a study to evaluate whether this holds true for dissolved organic matter (DOM), especially given the still mysterious origin of marine recalcitrant DOM. Here, characterization of DOM of 21 groundwater samples (depth 1-13 m, salinity 3.9‰ to 32.4‰) across a 65 m transect of an STE located in coastal Guangdong, China, has found systematic biotransformation toward "recalcitrant" carboxyl-rich alicyclic molecules (CRAM). The fraction of CRAM (%CRAM) increases from 33.1% to 76.7% with an increasing degree of DOM degradation and increasing salinity. Further, processing of DOM, including the more "biolabile" DOM with lower %CRAM released from aquitard, is more active under oxic conditions than under reducing conditions. Given the large quantities of sea water that recirculates through the sandy STEs globally, the amount of "recalcitrant" DOM (RDOM) entering the ocean after processing is likely to be considerable. While more studies are needed, the ocean can gain "recalcitrant" CRAM-like compounds in this way.