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Recent studies have highlighted the composition and complexity of dissolved organic matter (DOM) in glacial environments. Climate-induced changes to glacier runoff are projected to be an important source of DOM to coastal ecosystems. Photochemical and microbial (termed photo-biochemical) degradation of DOM would determine its fate on the glacier surface and in recipient coastal ecosystems. In order to understand the molecular imprints of photo-biochemical alteration of DOM, in situ field experiments were conducted over a period of 35 days in a coastal Antarctic site and DOM molecularly characterised using ultrahigh-resolution mass spectrometry. We show that the biogeochemistry of DOM is highly complex and intimately connected with microbial and photochemical processes operating individually or in combination. Photo-biochemical processes resulted in shifts in the nitrogen, sulfur, and phosphorous content of the DOM. These processes are also an important mechanism for transforming refractory DOM, like dissolved black carbon and carboxylic rich alicyclic molecules from the snow surface. This study is unique, as it provides new molecular-level information on compounds that comprise the photo- and bio-labile, photo- and bio-refractory, as well as photo- and bio-produced fractions of the supraglacial DOM pool. These insights into the interactions between microbes, light, and specific components of the DOM pool highlight the need for studies focused on the biogeochemistry of supraglacial carbon and its response to a changing climate.
