Optical and molecular characterization of dissolved organic matter (DOM) in the Arctic ice core and the underlying seawater (Cambridge Bay, Canada): Implication for increased autochthonous DOM during ice melting

Sea ice contains a large amount of dissolved organic matter (DOM), which can be released into the ocean once it melts. In this study, Arctic sea ice DOM was characterized for its optical (fluorescence) properties as well as the molecular sizes and composition via size exclusion chromatography and Fourier transformation ion cyclotron resonance mass spectrometry (FT-ICR MS). Ice cores were collected along with the underlying seawater samples in Cambridge Bay, an Arctic area experiencing seasonal ice formation. The ice core samples revealed a marked enrichment of dissolved organic carbon (DOC) compared to the seawater counterparts (up to 6.2 times greater). The accumulation can be attributed to in situ production by the autotrophic and heterotrophic communities. Fluorescence excitation emission matrices (EEMs) elaborated with parallel factor analysis (PARAFAC) evidenced the prevalence of protein-like substances in the ice cores, which likely results from in situ production followed by accumulation in the ice. Size exclusion chromatography further revealed the in situ production of all DOM size fractions, with the exception of the humic substance fraction. The majority of DOM in both the ice and seawater consists of low molecular weight compounds (<350 Da) probably derived by the microbial degradation/transformation of freshly produced DOM. Molecular characterization also supported the in situ production of DOM and highlighted the marked difference in molecular composition between sea ice and seawater. This study provides new insights into the possible role of sea ice DOM in the Arctic carbon cycle under climate change.