Search

Dissolved organic matter (DOM) is an omnipresent constituent of natural water bodies. Reuse and transformation of DOM compounds in the water column is driven by physicochemical and biological processes leading to the production of refractory DOM. Typically, breakdown of DOM chemical compounds into smaller or more condensed fragments is triggered by ultraviolet (UV) radiation. Here, we present a study on the photodegradation of DOM produced during an incubation experiment with a natural microbial community. At the end of the first incubation without UV irradiation, the samples from 3 mesocosms were filtered to remove microbes and particles and continuously exposed to UV radiation (280–365 nm). We investigated DOM in depth via monitoring of dissolved organic carbon (DOC) concentrations, DOM molecular characterization by Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and excitation emission matrix spectroscopy (EEMS). Analysis of variance indicated no significant differences in the DOC concentration between treatments. Main peaks in the fluorescent DOM (FDOM) were photo-bleached by UV radiation, and an increase in the fluorescent intensity of selected peaks was observed on irradiated samples toward the end of the experiment. Parallel factor analysis (PARAFAC) indicated the presence of three main components in all treatments: C1 (Marine humic M), C2 (Bacterial produced humic C), C3 (Tyrosine), and an additional component in the dark incubation of mesocosm 3, C4 (Tryptophan). Despite an intensive filtration protocol through 0.7, 0.2 and 0.1 μm filters, low bacterial abundances were determined (<2.5 × 10−3 cells mL−1). We observed a direct correlation between structural indices and the intensity of PARAFAC components. Average double bond equivalent and aromaticity were strongly positively correlated with PARAFAC components C1 and C2 for one or more mesocosm. Moreover, FT-ICR-MS showed that under the tested conditions, the refractory character of t

Natural organic matter (NOM) is a key parameter in aquatic biogeochemical processes. Part of the NOM pool exhibits optical properties, namely absorption and fluorescence. The latter is frequently utilized in laboratory measurements of its dissolved fraction (fluorescent dissolved organic matter, FDOM) through excitation–emission matrix spectroscopy (EEMS). We present the design and field application of a novel EEMS sensor system applicable in situ, the ‘Kallemeter’. Observations are based on a field campaign, starting in Norwegian coastal waters entering the Trondheimsfjord. Comparison against the bulk fluorescence of two commercial FDOM sensors exhibited a good correspondence of the different methods and the ability to resolve gradients and dynamics along the transect. Complementary laboratory EEM spectra measurements of surface water samples and their subsequent PARAFAC analysis revealed three dominant components while the ‘Kallemeter’ EEMS sensor system was able to produce reasonable EEM spectra in high DOM concentrated water bodies, yet high noise levels must be addressed in order to provide comparable PARAFAC components. Achievements and limitations of this proof-of-concept are discussed providing guidance towards full in situ EEMS measurements to resolve rapid changes and processes in natural waters based on the assessment of spectral properties. Their combination with multiwavelength FDOM sensors onboard autonomous platforms will enhance our capacities in observing biogeochemical processes in the marine environment in spatiotemporal and spectral dimensions.