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We have investigated the bacterial decomposition of dissolved organic matter (DOM) extracted from the organic layer of a boreal forest soil and filtered at a pore size of 0.2 mu m. This DOM source has previously been extensively characterized and contains approximately equal amounts by carbon of a colloidal fraction, mainly composed of carbohydrates, and a fraction of molecularly dissolved DOM. Here, extracts were inoculated with soil bacteria and the decomposition of DOM was followed over a period of 2 months, during which it was analyzed with scattering methods and H-1 NMR, and by measuring the concentration of total organic carbon. A comparison was also made with dialyzed extract. Results showed that while the bacteria fully decomposed the molecular fraction within approximately two weeks, the colloidal fraction was stable with no visible decomposition within the 2 months. The results indicate the importance of distinguishing small molecules from colloidal aggregates in decomposition studies, and demonstrate the usefulness of combining scattering methods with ¹H NMR for this purpose.

Photochemical degradation of dissolved organic matter (DOM) has been the subject of numerous studies; however, its regulation along the inland water continuum is still unclear. We aimed to unravel the DOM photoreactivity and concurrent DOM compositional changes across 30 boreal aquatic ecosystems including peat waters, streams, rivers, and lakes distributed along a water residence time (WRT) gradient. Samples were subjected to a standardized exposure of simulated sunlight. We measured the apparent quantum yield (AQY), which corresponds to DOM photomineralization per photon absorbed, and the compositional change in DOM at bulk and individual compound levels in the original samples and after irradiation. AQY increased with the abundance of terrestrially derived DOM and decreased at higher WRT. Additionally, the photochemical changes in both DOM optical properties and molecular composition resembled changes along the natural boreal WRT gradient at low WRT (<3 years). Accordingly, mass spectrometry revealed that the abundance of photolabile and photoproduced molecules decreased with WRT along the boreal aquatic continuum. Our study highlights the tight link between DOM composition and DOM photodegradation. We suggest that photodegradation is an important driver of DOM composition change in waters with low WRT, where DOM is highly photoreactive.

Aquatic dissolved organic matter (DOM) is a crucial component of the global carbon cycle, and the extent to which DOM escapes mineralization is important for the transport of organic carbon from the continents to the ocean. DOM persistence strongly depends on its molecular properties, but little is known about which specific properties cause the continuum in reactivity among different dissolved molecules. We investigated how DOM fractions, separated according to their hydrophobicity, differ in biodegradability across three different inland water systems. We found a strong negative relationship between hydrophobicity and biodegradability, consistent for the three systems. The most hydrophilic fraction was poorly recovered by solid-phase extraction (SPE) (3-28% DOC recovery) and was thus selectively missed by mass spectrometry analysis during SPE. The change in DOM composition after incubation was very low according to SPE-ESI (electrospray ionization)-mass spectrometry (14% change, while replicates had 11% change), revealing that this method is sub-optimal to assess DOM biodegradability, regardless of fraction hydrophobicity. Our results demonstrate that SPE-ESI mass spectrometry does not detect the most hydrophilic and most biodegradable species. Hence, they question our current understanding of the relationships between DOM biodegradability and its molecular composition, which is built on the use of this method.

Streams and rivers form an important link in the global carbon cycle by transporting and transforming large amounts of carbon imported from terrestrial ecosystems to the oceans. Since streams in agricultural areas often experience increased concentrations of suspended mineral particles from soil erosion, they are important sites where dissolved organic carbon (DOC) may be adsorbed to particles and retained in the sediment. As the extent of adsorption varies with the molecular composition of dissolved organic matter (DOM), which is seasonally variable, we expect also the fraction of organic material that adsorbs to mineral particles to fluctuate over time. We sampled the agriculturally impacted River Fyrisån (Sweden) monthly during 1 year, and measured DOC concentration and DOM composition based on several optical properties. At each sampling occasion, we estimated the potential for adsorption by exposing the samples to a reference clay. The potential for adsorption was greatest when riverine DOM had the most terrestrial character, as this fraction of the DOM pool was selectively adsorbed to clay surfaces. The extent of adsorption was negatively related to the concentration of base cations, most notably calcium. We suggest that the observed relationships between the potential for adsorption, DOM composition and base cations are linked by discharge. A bioavailability test at one sampling occasion suggested that DOM remaining after exposure to clay particles was more biodegradable. This implies that adsorption may alter the degradation potential of DOM remaining in solution, which could have far reaching effects on the fate of organic carbon.

Fluorescence is an easily available analytical technique used to assess the optical characteristics of dissolved organic matter (DOM). Despite widespread use, there has been some confusion about how robust fluorescence spectroscopy is to differences in solution pH. Here we assess fluorescence characteristics of three natural water samples and one commercially available standard (Nordic Reservoir) by modifying the pH across a range from 3.5 to 9.0 at 0.5 pH increments. We used two statistical approaches to assess if fluorescence intensity shifted significantly across this pH range. We identified that humic-like and protein-like fluorescence was largely stable within the pH range of 5.5 to 7.5, which represents 80% of Swedish lakes and streams. Likewise, we found that the three commonly used fluorescence indices were robust across the full pH range tested with the exception of the humification index, which had a narrower range of stability. The commerical humic substance sample was highly unstable with changes to pH in the regions of protein-like fluorescence being particularly sensitive. One of our conclusions is that differences in fluorescence intensity in the pH range of 5.5 to 7.5, typical for most inland waters, are generally minor. We recommend adjusting the pH when samples fall outside this region and to be especially careful in interpreting results from commercial humic substances.

Inland waters receive and process large amounts of colored organic matter from the terrestrial surroundings. These inputs dramatically affect the chemical, physical, and biological properties of water bodies, as well as their roles as global carbon sinks and sources. However, manipulative studies, especially at ecosystem scale, require large amounts of dissolved organic matter with optical and chemical properties resembling indigenous organic matter. Here, we compared the impacts of two leonardite products (HuminFeed and SuperHume) and a freshly derived reverse osmosis concentrate of organic matter in a set of comprehensive mesocosm- and laboratory-scale experiments and analyses. The chemical properties of the reverse osmosis concentrate and the leonardite products were very different, with leonardite products being low and the reverse osmosis concentrate being high in carboxylic functional groups. Light had a strong impact on the properties of leonardite products, including loss of color and increased particle formation. HuminFeed presented a substantial impact on microbial communities under light conditions, where bacterial production was stimulated and community composition modified, while in dark potential inhibition of bacterial processes was detected. While none of the browning agents inhibited the growth of the tested phytoplankton Gonyostomum semen, HuminFeed had detrimental effects on zooplankton abundance and Daphnia reproduction. We conclude that the effects of browning agents extracted from leonardite, particularly HuminFeed, are in sharp contrast to those originating from terrestrially derived dissolved organic matter. Hence, they should be used with great caution in experimental studies on the consequences of terrestrial carbon for aquatic systems.

Inland waters receive organic matter from terrestrial ecosystems and in situ production. In transit from land to the ocean, dissolved organic carbon (DOC) may be mineralised to inorganic forms (CO₂ and CH₄) by microbial degradation and photodegradation. It may also transition from dissolved into particulate phase, and be transferred to the sediment and buried. One way in which this can happen is by adsorption of dissolved organic matter (DOM) to mineral particles. This process is rarely studied in inland waters, since suspended particles are often in short supply. However, there are scenarios under which high particle concentrations occur, and in those cases, adsorption may have a substantial effect on DOM composition and reactivity. The overall aim of this thesis was to investigate the potential for DOM adsorption to inorganic particles and the resulting effect on DOM composition, as well as its biological reactivity. Three studies within this thesis focus on different types of surfaces waters in the boreal landscape of Sweden, and one study focuses on coastal moorland streams in the United Kingdom. Adsorption experiments were conducted under controlled laboratory conditions using batch experiments. DOM quality was studied based on bulk optical properties, and composition was examined by high resolution mass spectrometry. Adsorption experiments using a commercially available reference clay (containing substantial amounts of aluminium and iron oxides) as the adsorbent show a widespread potential for DOM in inland water to adsorb to mineral particles. The extent of DOM adsorption in the experiments was regulated by two factors: 1) DOM composition, since compounds with a terrestrial signature were selectively adsorbed, and 2) water chemistry, as adsorption was impaired by pH>7 and higher concentrations of base cations. These general patterns were observed across surface waters with contrasting DOC concentrations, DOM composition and water chemistry parameters, and across spatial and temporal scales. In contrast, adsorption to suspended sediment derived from a glacial stream resulted in the removal of ‘protein-like’ DOM that is produced in situ, rather than terrestrially derived DOM. Hence, the mineralogy of particles may determine which DOM fraction is adsorbed. Experiments examining microbial degradation indicated that the effect of adsorption on the bioavailability of the remaining DOM depends on which DOM fraction is removed by the different adsorbents. This thesis shows that adsorption to mineral particles in aquatic ecosystems is a highly relevant biogeochemical process that has the potential to alter DOM composition and thereby affect its biological reactivity. 

Different processes contribute to the loss or transformation of dissolved organic matter (DOM) and change DOM concentration and composition systematically along the inland water continuum. Substantial efforts have been made to estimate the importance of microbial and photochemical degradation for DOM concentration and composition and, to some extent, also DOM losses by flocculation, whereas the significance of DOM adsorption to inorganic surfaces has received less attention. Hence, knowledge on the possible extent of adsorption, its effect on DOM loads and composition and on where along the aquatic continuum it might be important, is currently limited or lacking altogether. Here we experimentally determine DOM adsorption onto mineral particles in freshwater ecosystems covering a water residence time gradient in boreal landscape Sweden. We hypothesized that adsorption would gradually decrease with increasing water residence time but actually found that DOM is highly susceptible to adsorption throughout the aquatic continuum. Mass spectrometry and fluorescence analysis on DOM suggest that freshly produced aquatic DOM is less susceptible to adsorption than more terrestrial material. Moreover, the percentage DOM adsorbed in the experiments greatly exceeds the actual adsorption taking place in boreal inland waters across all studied systems. These results illustrate the potential impact of mineral erosion, for example, as a result of agriculture, mining or forestry practices, on the availability, transport, and composition of organic carbon in inland waters.

Different processes contribute to the loss or transformation of dissolved organic matter (DOM) and change DOM concentration and composition systematically along the inland water continuum. Substantial efforts have been made to estimate the importance of microbial and photochemical degradation for DOM concentration and composition and, to some extent, also DOM losses by flocculation, whereas the significance of DOM adsorption to inorganic surfaces has received less attention. Hence, knowledge on the possible extent of adsorption, its effect on DOM loads and composition and on where along the aquatic continuum it might be important is currently limited or lacking altogether. Here, we experimentally determine DOM adsorption onto mineral particles in freshwater ecosystems covering a water residence time gradient in boreal landscape Sweden. We hypothesized that adsorption would gradually decrease with increasing water residence time, but actually found that DOM is highly susceptible to adsorption throughout the aquatic continuum. Mass spectrometry and fluorescence analysis on DOM suggest that freshly produced aquatic DOM is less susceptible to adsorption than more terrestrial material. Moreover, the percentage DOM adsorbed in the experiments greatly exceeds the actual adsorption taking place in boreal inland waters across all studied systems. These results illustrate the potential impact of mineral erosion, for example as a result of agriculture, mining or forestry practices, on the availability, transport and composition of organic carbon in inland waters.