Molecular level characterization of supraglacial dissolved organic matter sources and exported pools the southern Greenland Ice Sheet.

During the ablation season, active microbial communities colonise large areas of the Greenland Ice Sheet surface and produce dissolved organic matter (DOM) that may be exported downstream by surface melt. Meltwater flow through the bare ice interfluvial area, characterized by a porous weathering crust, is slow (~ 10-2 m d-1), meaning that it presents a potential site for photochemical and/or microbial alteration of supraglacial DOM. Transformations of supraglacial DOM during transport through the supraglacial drainage system remain unexplored, limiting our understanding of supraglacial DOM inputs to downstream subglacial and coastal ecosystems. Here, we employ negative-ion electrospray ionization 21 tesla Fourier transform ion cyclotron resonance mass spectrometry to catalogue the molecular composition of DOM in supraglacial dark ice, weathering crust meltwater, and supraglacial stream water sampled in a hydrologically connected supraglacial micro- catchment to address this knowledge gap. Dark ice DOM contained significantly more aromatic (25 ± 3 %) and less biolabile (13 ± 4 %) DOM than weathering crust meltwater (3 ± 0 and 50 ± 0 %, respectively), pointing to retention of DOM on the ice surface and microbial, as well as photochemical alteration of DOM during transit through the supraglacial drainage system. These findings have implications for our understanding of supraglacial biogeochemical cycling, highlighting the importance of including the weathering crust photic zone when assessing supraglacial inputs to subglacial and downstream ecosystems. [ABSTRACT FROM AUTHOR]