Assessing the Role of Photochemistry in Driving the Composition of Dissolved Organic Matter in Glacier Runoff

Abstract

Dissolved organic matter (DOM) in glacier runoff is aliphatic-rich, yet studies have proposed that DOM originates mainly from allochthonous, aromatic, and often aged material. Allochthonous organic matter (OM) is exposed to ultraviolet radiation both in atmospheric transport and post-deposition on the glacier surface. Thus, we evaluate photochemistry as a mechanism to account for the compositional disconnect between allochthonous OM sources and glacier runoff DOM composition. Six endmember OM sources (including soils and diesel particulate matter) were leached and photo-irradiated for 28 days in a solar simulator, until >90% of initial chromophoric DOM was removed. Ultrahigh-resolution mass spectrometry was used to compare the molecular composition of endmember leachates pre- and post-irradiation to DOM in supraglacial and bulk runoff from the Greenland Ice Sheet and Juneau Icefield (Alaska), respectively. Photoirradiation drove molecular level convergence between the initially aromatic-rich leachates and aromatic-poor glacial samples, selectively removing aromatic compounds (−80 ± 19% relative abundance) and producing aliphatics (+75 ± 35% relative abundance). Molecular level glacier runoff DOM composition was statistically indistinguishable to post-irradiation leachates. Bray-Curtis analysis showed substantial similarity in the molecular formulae present between glacier samples and post-irradiation leachates. Post-irradiation leachates contained 84 ± 7.4% of the molecular formulae, including 72 ± 17% of the aliphatic formulae, detected in glacier samples. Our findings suggest that photodegradation, either in transit to or on glacier surfaces, could provide a mechanistic pathway to account for the disconnect between proposed aromatic, aged sources of OM and the aliphatic-rich fingerprint of glacial DOM.