Advances in spectroscopic techniques have led to an increase in the use of optical properties (absorbance and fluorescence) to assess dissolved organic matter (DOM) composition and infer sources and processing. However, little information is available to assess the impact of biological and photolytic processing on the optical properties of original DOM source materials. Over a 3.5 month laboratory study, we measured changes in commonly used optical properties and indices in DOM leached from peat soil, plants, and algae following biological and photochemical degradation to determine whether they provide unique signatures that can be linked to original DOM source. Changes in individual optical parameters varied by source material and process, with biodegradation and photodegradation often causing values to shift in opposite directions. Although values for different source materials frequently overlapped, multivariate statistical analyses showed that unique optical signatures could be linked to original DOM source material, with 17 optical properties determined by discriminant analysis to be significant (p < 0.05) in distinguishing between DOM source and environmental processing. These results demonstrate that inferring source material from optical properties is possible when parameters are evaluated in combination even after extensive biological and photochemical alteration.

https://aslopubs.onlinelibrary.wiley.com/doi/epdf/10.1002/lno.10270

Optical properties of dissolved organic matter (DOM): Effects of biological and photolytic degradation

Advances in water chemistry in the last decade have improved our knowledge about the genesis, com- position, and structure of dissolved organic matter, and its effect on the environment. Improvements in analyti- cal technology, for example Fourier-transform ion cyclo- tron (FT-ICR) mass spectrometry (MS), homo and hetero-correlated multidimensional nuclear magnetic res- onance (NMR) spectroscopy, and excitation emission matrix fluorimetry (EEMF) with parallel factor (PARAFAC) analysis for UV-fluorescence spectroscopy have resulted in these advances. Improved purification methods, for example ultrafiltration and reverse osmosis, have enabled facile desalting and concentration of fresh- ly collected DOM samples, thereby complementing the analytical process. Although its molecular weight (MW) remains undefined, DOM is described as a complex mixture of low-MW substances and larger-MW biomo- lecules, for example proteins, polysaccharides, and exo- cellular macromolecules. There is a general consensus that marine DOM originates from terrestrial and marine sources. A combination of diagenetic and microbial processes contributes to its origin, resulting in refractory organic matter which acts as carbon sink in the ocean. Ocean DOM is derived partially from humified products of plants decay dissolved in fresh water and transported to the ocean, and partially from proteinaceous and poly- saccharide material from phytoplankton metabolism, which undergoes in-situ microbial processes, becoming refractory. Some of the DOM interacts with radiation and is, therefore, defined as chromophoric DOM (CDOM). CDOM is classified as terrestrial, marine, anthropogenic, or mixed, depending on its origin. Ter- restrial CDOM reaches the oceans via estuaries, whereas autochthonous CDOM is formed in sea water by micro- bial activity; anthropogenic CDOM is a result of human activity. CDOM also affects the quality of water, by shielding it from solar radiation, and constitutes a car- bon sink pool. Evidence in support of the hypothesis that part of marine DOM is of terrestrial origin, being the result of a long-term carbon sedimentation, has been obtained from several studies discussed herein.

Molecular characterization of dissolved organic matter (DOM): a critical review

Surface water samples were collected from 43 streams distributed throughout watersheds of mixed land use in southern Ontario, Canada. Absorbance and fluorescence spectroscopy with parallel factor analysis (PARAFAC) was used to characterize dissolved organic matter (DOM). DOM characteristics were related to environmental variables, microbial activity indicators (bacterial production and extracellular leucine aminopeptidase activity), and riparian land use to understand better how these factors influence DOM in streams. PARAFAC produced a six-component model (C1 to C6). Temperature correlated with each PARAFAC component, suggesting that water source, drainage area, and light penetration broadly affected DOM characteristics. C1 and C2 represented terrestrial, humic-like DOM fluorophore groups and comprised 41–65% of stream DOM fluorescence. C5, a tryptophan-like component, related negatively to a humification index but positively to leucine-aminopeptidase activity and recently produced DOM, suggesting that C5 consisted of autochthonous, microbially produced DOM. C3, C4, and C6 showed signs of quinone-like, humic-like, and microbial transformable fluorophores. The distribution of these potentially redox-active PARAFAC components indicated that DOM was in a more reduced state in streams with higher bacterial production and agricultural land use than in streams with increased wetlands area, which had greater relative abundance of the oxidized quinone-like component. Anthropogenic land use and microbial activity altered the quantity and quality of DOM exported from human-affected streams from that observed in forest- and wetland-dominated streams. DOM in agriculturally affected streams was likely more labile and accessible to the microbial community than DOM in wetland streams, which supported low rates of microbial activity.

https://aslopubs.onlinelibrary.wiley.com/doi/pdf/10.4319/lo.2010.55.3.1159

Unraveling the role of land use and microbial activity in shaping dissolved organic matter characteristics in stream ecosystems

https://research.birmingham.ac.uk/portal/files/40126586/Carstea_et_al_in_press.pdf

Fluorescence spectroscopy for wastewater monitoring: a review

Characterization of dissolved organic matter in cave and spring waters using UV–Vis absorbance and fluorescence spectroscopy

Properties of fluorescent dissolved organic matter in the Gironde Estuary

New insights into the size distribution of fluorescent dissolved organic matter in estuarine waters

Combined 3D-spectrofluorometry, high performance liquid chromatography and capillary electrophoresis for the characterization of dissolved organic matter in natural waters

Lilian Vacher

Papers

Properties of fluorescent dissolved organic matter in the Gironde Estuary

New insights into the size distribution of fluorescent dissolved organic matter in estuarine waters

Combined 3D-spectrofluorometry, high performance liquid chromatography and capillary electrophoresis for the characterization of dissolved organic matter in natural waters