Fast-freezing with liquid nitrogen preserves bulk dissolved organic matter concentrations, but not its composition

Abstract. Freezing can affect concentrations and spectroscopic properties of dissolved organic matter (DOM) in water samples. Nevertheless, water samples are regularly frozen for sample preservation. In this study we tested the effect of different freezing methods (standard freezing at −18 °C and fast-freezing with liquid nitrogen) on DOM concentrations measured as organic carbon (DOC) concentrations and on spectroscopic properties of DOM from different terrestrial ecosystems (forest and grassland). Fresh and differently frozen throughfall, stemflow, litter leachate and soil solution samples were analyzed for DOC concentrations, UV-vis absorption and fluorescence excitation–emission matrices combined with parallel factor analysis (PARAFAC). Fast-freezing with liquid nitrogen prevented a significant decrease of DOC concentrations observed after freezing at −18 °C. Nonetheless, the share of PARAFAC components 1 (EX_max < 250 nm (340 nm), EX_max: 480 nm) and 2 (EX_max: 335 nm, EX_max: 408 nm) to total fluorescence and the humification index (HIX) decreased after both freezing treatments, while the shares of component 3 (EX_max: < 250 nm (305 nm), EX_max: 438 nm) as well as SUVA₂₅₄ increased. The contribution of PARAFAC component 4 (EX_max: 280 nm, EX_max: 328 nm) to total fluorescence was not affected by freezing. We recommend fast-freezing with liquid nitrogen for preservation of bulk DOC concentrations of samples from terrestrial sources, whereas immediate measuring is preferable to preserve spectroscopic properties of DOM.