Northern peatlands represent a significant carbon reservoir, containing approximately a third of the terrestrial carbon pool. The stability of these carbon stores is poorly understood, and processes of accumulation and degradation appear to be finely balanced. Over the last decade, it has become increasingly clear that losses of dissolved organic carbon (DOC) from peatlands can be of considerable size and this flux appears to have increased substantially over the last 20 years. Despite its significance, the chemical composition of peatland-derived DOC remains poorly understood. This study aimed to characterise dissolved organic matter (DOM) at the molecular level using a novel combination of techniques. The study site (Cors Fochno, Wales, UK) is an ombrotrophic bog on which a number of studies into carbon cycling and hydrology have been carried out, providing a useful context for this project. The size and compositions of the DOC pool was monitored over 18 months, from three banks of piezometers, sampling from depths of 15 cm to 6 m. DOM which is representative of bog runoff was also monitored. DOC concentrations varied considerably between locations, spanning an order of magnitude (11.4 to 114 mgC l-1). Several relationships between DOC concentration and environmental and physical factors were established: DOC levels near the surface of the peatland varied with temperature, those in the runoff were most affected by recent rainfall events and the apparent DOC concentration at depth was related to the hydraulic conductivity of peat at that depth. The annual flux of DOC from the site was estimated at 113 tonnes, or 17.4 gC m-2. Only a small portion of the DOC pool could be characterised by analysis of dissolved combined amino acids (DCAA) and dissolved carbohydrates (as neutral sugars). Non-protein amino acids were most abundant in runoff samples, suggesting microbial reworking of DOM on entering drainage systems. DCAA yields decreased with depth, and the DCAA pool in deeper peat layers was characterised by more hydrophobic compounds. Interpretation of semi-quantitative results from TMAH thermochemolysis GC-MS analysis suggested oxidative degradation of organic matter near the surface of the peatland and photochemical degradation where DOM entered drainage networks, and this was supported by novel interpretation of results from ultrahigh resolution mass spectrometry analysis. The deepest porewaters were dominated by nalkanes, with notable contributions from fatty acids, suggesting a plant wax source for this DOM. The highest DOC concentrations were found at intermediate depth from a site midway between the centre of the bog and the southern boundary where hydraulic conductivities were low, and DOM from these piezometers were characterised by high contributions from a suite of phenolic compounds (with mainly para-hydroxyphenyl structures). These compounds have been linked to Sphagnum species, and are known to be functionally important to the development and maintenance of the unusual chemical environment in peatlands which slows decay rates, reduces microbial activity, and allows the sequestration of the large carbon reservoir. The findings of this study highlight the dynamic nature of peatland derived DOM, both in the size of the carbon pool and its composition which change dramatically with both season and depth.

Increased DOC and Fe concentrations from terrestrial landscapes has led to the browning of boreal surface waters. The negative societal and ecological impacts of brownification are increased cost of water purification, increased presences of algae and cyanobacteria, loss of ecosystem services and reduced recreational value. Impacts of climate change, changes in land use and reduced sulfur deposition have been identified as drivers of brownification. While it has been recognized that DOC and Fe from terrestrial landscapes is increasing, little has been done to understand the impact of different land use practices on brownification. This research aims at evaluating the DOC and Fe runoff from spruce plantations, clear-cuts and wetland landscapes and determining the export of DOC from these landscapes into humic lakes. To do that, streams running through these three different land use types were sampled for water colour, pH, temperature, conductivity, DOC and Fe both at upstream and downstream of each land use type. Further, water discharge was calculated with the help of flow speed measurements and stream profiling (width, depth and channel shape). DOC (but not Fe) concentrations changed significantly depending on land use type. Wetlands lead to reduced DOC concentrations, whereas especially spruce plantations lead to increased stream water DOC concentrations.

Snowmelt river systems exhibit seasonal fluxes in water chemistry, potentially affecting the water supply of one-sixth of the worlds population. In this study, we examined water chemistry of the upper Provo River, northern Utah, which supplies water to over two million people along the urban Wasatch Front. Seasonal changes in water chemistry were characterized by analyzing discharge and dissolved organic carbon (DOC) with dissolved trace metal and cation concentrations (La, Pb, Cu, Al, Be, Sr and K) over three consecutive water years 20142016, with intensive sampling during snowmelt runoff. To better understand links between metal movement and DOC, we sampled the river in three locations (Soapstone, Woodland, and Hailstone), snowpack, and ephemeral snowmelt channels. Concentrations of La, Pb, Cu, Al, and Be increased with discharge/snowmelt during the 2014, 2015 and 2016 water years. Over 90% of La, Pb, Cu, Al, Be and between 70-90% Sr and K loads occurred during the snowmelt season (April-June). In relation to discharge, concentrations of each element varied between the river sampling sites. At Soapstone, DOC, La, Pb, Cu, Al and Be increased slightly with discharge, but Sr and K remained chemostatic. At Woodland and Hailstone, DOC, La, Pb, Cu, Al and Be had sharp increases with discharge, and Sr and K were diluted. Hysteresis patterns showed that concentrations of DOC, La, Pb, Cu, Al, Be, Sr and K all peaked on the rising limb of the hydrograph at the higher elevation Soapstone site but patterns were variable at the lower elevation Woodland and Hailstone sites. Concentrations for ephemeral channels were significantly higher than river and snow concentrations in La, Pb, Cu and Al, suggesting soil water was a significant source of flushed metals and DOC to the upper Provo River. DOC was highly correlated with La (R2 = 0.94, P = < .0001), Pb (R2 = 0.76, P = < .0023), Cu (R2 = 0.83, P = < .0001), Al (R2 = 0.94, P = < .0001) and Be (R2 = 0.93, P = < .0005), and likely facilitating metal transport. More work is needed to determine the mechanisms of DOC and metal transport, and potential metal complexation. This study has implications for understanding water quality impacts from metal flushing during snowmelt in mountain watersheds.

Snowmelt river systems exhibit seasonal fluxes in water chemistry, potentially affecting the water supply of one-sixth of the worlds population. In this study, we examined water chemistry of the upper Provo River, northern Utah, which supplies water to over two million people along the urban Wasatch Front. Seasonal changes in water chemistry were characterized by analyzing discharge and dissolved organic carbon (DOC) with dissolved trace metal and cation concentrations (La, Pb, Cu, Al, Be, Sr and K) over three consecutive water years 2014”2016, with intensive sampling during snowmelt runoff. To better understand links between metal movement and DOC, we sampled the river in three locations (Soapstone, Woodland, and Hailstone), snowpack, and ephemeral snowmelt channels. Concentrations of La, Pb, Cu, Al, and Be increased with discharge/snowmelt during the 2014, 2015 and 2016 water years. Over 90% of La, Pb, Cu, Al, Be and between 70-90% Sr and K loads occurred during the snowmelt season (April-June). In relation to discharge, concentrations of each element varied between the river sampling sites. At Soapstone, DOC, La, Pb, Cu, Al and Be increased slightly with discharge, but Sr and K remained chemostatic. At Woodland and Hailstone, DOC, La, Pb, Cu, Al and Be had sharp increases with discharge, and Sr and K were diluted. Hysteresis patterns showed that concentrations of DOC, La, Pb, Cu, Al, Be, Sr and K all peaked on the rising limb of the hydrograph at the higher elevation Soapstone site but patterns were variable at the lower elevation Woodland and Hailstone sites. Concentrations for ephemeral channels were significantly higher than river and snow concentrations in La, Pb, Cu and Al, suggesting soil water was a significant source of flushed metals and DOC to the upper Provo River. DOC was highly correlated with La (R2 = 0.94, P = <<> .0001), Pb (R2 = 0.76, P = <<> .0023), Cu (R2 = 0.83, P = <<> .0001), Al (R2 = 0.94, P = <<> .0001) and Be (R2 = 0.93, P = <<> .0005), and likely facilitating metal transport. More work is needed to determine the mechanisms of DOC and metal transport, and potential metal complexation. This study has implications for understanding water quality impacts from metal flushing during snowmelt in mountain watersheds.

Of the organic matter in soils typically < 1% by weight is dissolved in the soil solution (dissolved organic matter; DOM). DOM is a continuum of molecules of various sizes and chemical structures which has largely been operationally defined as the fraction of total organic carbon in an aqueous solution that passes through a 0.45 µm filter. Although only representing a relatively small proportion, it represents the most mobile part of soil organic carbon and is probably enriched with highly labile compounds. DOM acts as a source of nutrients for both soil and aquatic micro-organisms, influences the fate and transport of organic and inorganic contaminants, presents a potential water treatment problem and may indicate the mobilisation rate of key terrestrial carbon stores. The objective of this research was to ascertain some of the biologically relevant characteristics of soil DOM and specifically to determine: (1) the influence of method and time of extraction of DOM from the soil on its biochemical composition and concentration; (2) the dynamics of DOM biodegradation; and, (3) the effects of repeated applications of trace amounts of DOM on the rate of soil carbon mineralization. To examine the influence of method and time of extraction on the composition and concentration of DOM, soil solution was collected from a raised peat bog in Central Scotland using water extraction, field suction lysimetry, and centrifugation techniques on a bimonthly basis over the period of a year (Aug 2003 – Jun 2004). Samples were analysed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), protein, carbohydrate and amino acid content. For all of the sampled months except June the biochemical composition of DOC varied with extraction method, suggesting the biological, chemical and/or physical influences on DOC production and loss are different within the differently sized soil pores. Water-extractable DOC generally contained the greatest proportion of carbohydrate, protein and/or amino acid of the three extraction methods. Time of extraction had a significant effect on the composition of water- and suction-extracted DOC: the total % carbohydrate + protein + amino acid C was significantly higher in Oct than Dec, Feb and Jun for water-extracted DOC and significantly greater in Dec than Aug, Apr and Jun for suction-extracted DOC. There was no significant change in the total % carbohydrate + protein + amino acid C of centrifuge-extracted DOC during the sampled year. Time of extraction also had a significant effect on the % protein + amino acid N in water- and centrifuge-extracted DON: Oct levels were significantly higher than Feb for water-extracted DON and significantly higher in Aug and Apr for centrifuge-extracted DON. Concentrations of total DOC and total DON were also found to be dependent on time of extraction. DOC concentrations showed a similar pattern of variation over the year for all methods of extraction, with concentrations relatively constant for most of the year, rising in April to reach a peak in Jun. DON concentrations in water- and centrifuge-extracted DON peaked later, in Aug. There were no significant seasonal changes in the concentration of suction-extracted DON. A lack of correlation between DOC and DON concentrations suggested that DOC and DON production and/or loss are under different controls. Laboratory-based incubation experiments were carried out to examine the dynamics of DOC biodegradation. Over a 70 day incubation period at 20oC, the DOM from two types of peat (raised and blanket) and four samples of a mineral soil (calcaric gleysol), each previously exposed to a different management strategy, were found to be comprised of a rapidly degradable pools (half-life: 3 – 8 days) and a more stable pool (half-life: 0.4 to 6 years). For all soil types/treatments, excepting raised peat, the total net loss of DOC from the culture medium was greater than could be accounted for by the process of mineralization alone. A comparison between net loss of DOC and loss of DOC to CO2 and microbial biomass determined by direct microscopy suggested that at least some of the differences between DOC mineralised and net DOC loss were due to microbial assimilation and release. Changes in the microbial biomass during the decomposition process showed proliferation followed by decline over 15 days. The protein and carbohydrate fractions showed a complex pattern of both degradation and production throughout the incubation. The effects of repeated applications of trace amounts of litter-derived DOC on the rate of carbon mineralization over a 35 day period were investigated in a laboratory based incubation experiment. The addition of trace amounts of litter-derived DOC every 7 and 10.5 days appeared to ‘trigger’ microbial activity causing an increase in CO2 mineralisation such that extra C mineralised exceeded DOC additions by more than 2 fold. Acceleration in the rate of extra C mineralised 7 days after the second addition suggested that either the microbial production of enzymes responsible for biodegradation and/or an increase in microbial biomass, are only initiated once a critical concentration of a specific substrate or substrates has been achieved. The addition of ‘DOC + nutrients’ every 3.5 days had no effect on the total rate of mineralization. To date DOC has tended to be operationally defined according to its chemical and physical properties. An understanding of the composition, production and loss of DOC from a biological perspective is essential if we are to be able to predict the effects of environmental change on the rate of mineralization of soil organic matter. This research has shown that the pools of DOC extracted, using three different methods commonly used in current research, are biochemically distinct and respond differently to the seasons. This suggests some degree of compartmentalisation of biological processes within the soil matrix. The observed similarities between the characteristics of the decomposition dynamics of both peatland and agricultural DOC suggests that either there is little difference in substrate quality between the two systems or that the microbial community have adapted in each case to maximise their utilisation of the available substrate. The dependency of the concentration and biochemical composition of DOC on the seasons requires further work to ascertain which biotic and/or abiotic factors are exerting control. Published research has focussed on factors such as temperature, wet/dry cycles, and freeze/thawing. The effect of the frequency of doses of trace amounts of DOC on increasing the rate of soil organic C mineralization, evident from this research, suggests that the interval between periods of rainfall may be relevant. It also emphasises how it can be useful to use knowledge of a biological process as the starting point in determining which factors may be exerting control on DOC production and loss.

This research combines observation, experimentation, and modeling to evaluate the influence of lakes on dissolved organic matter (DOM) quantity, quality and export in subalpine watersheds of the Sawtooth Mountain Lake District, central Idaho. First, I conducted an empirical study of the hydrologic and biogeochemical controls on DOM dynamics in stream-lake fluvial networks. I hypothesized that lakes would decrease temporal variability (i.e., buffer) and alter the characteristics of DOM from inflow to outflow. I tested these hypotheses by evaluating DOM temporal patterns and measuring annual export in seven-paired lake inflows and outflows. I then evaluated how ultraviolet (UV) exposure affected DOM characteristics during snowmelt and baseflow, and how UV alters baseflow DOM bioavailability and nutrient limitation. Given that increased water residence time increases UV exposure, I hypothesized that lake outflow DOM would be more photorecalcitrant than DOM from lake inflows. I further hypothesized that UV exposure would increase DOM quality, heterotrophic processing, and nutrient demand. Results indicate that lakes can buffer stream temporal variability by acting as a DOM sink during snowmelt and a DOM source during baseflow. Lake outflow DOM photodegradation was similar to lake inflows during snowmelt (p=0.66). Conversely, outflow DOM was 2X more photorecalcitrant than inflow DOM during baseflow (ANOVA, p=0.03) and was strongly related to water residence time (WRT). During baseflow, light exposure increased inflow and outflow DOM bioavailability (p=0.059 and 0.024, respectively) and nutrient limitation (p=0.03 and 0.09, respectively). Combined, these results indicate that WRT in subalpine lakes strongly influences DOM temporal variability and DOM degradation and processing. Thus, lakes can provide temporal stability of DOM and potentially increase both carbon and nutrient uptake by heterotrophs in lake outflows. I then evaluated how global changes could alter hydrologic and nutrient dynamics in a subalpine lake. Model results indicate that the magnitude and timing of snowmelt runoff can have a substantial effect on water and nutrient exports. In phosphorus (P)-limited lakes, increases in inorganic N concentrations within and exported from lakes are likely to occur with increased temperatures and lake WRT. Increases in atmospheric N deposition will further enhance inorganic N exports in P-limited subalpine lakes.

Austräge von gelöstem organischem Kohlenstoff (DOC) aus Mooren sind aus Gründen des Klima- und Trinkwasserschutzes unerwünscht. Einflüsse von Landnutzung auf die Höhe der DOC-Konzentrationen werden teilweise inkonsistent beschrieben und überdies sind wenige Angaben zu den stark anthropogen überprägten Niedermooren Nordostdeutschlands verfügbar. Daher sind in der vorliegenden Arbeit Zusammenhänge von Management und Standorteigenschaften zu DOC-Konzentrationen auf Lysimeter- und Freilandebene untersucht worden. Es zeigte sich, dass die DOC-Gehalte des wiedervernässten Niedermoores deutlich und die DOC-Austräge tendenziell geringer waren als am landwirtschaftlich genutzten Standort, und dass die DOC-Konzentrationen im Grabenwasser seit der Wiedervernässung gesunken sind. Die unmittelbar durch Landnutzung beeinflussten Parameter Wasserstand und Vegetation waren in Lysimeterversuchen von untergeordneter Bedeutung. Niedermoore scheinen bedingt durch ihre individuelle Genese ein spezifisches DOC-Potential bzw. einen „Fingerabdruck“ zu haben, weshalb bei Wiedervernässung zwar sinkende, aber nicht unbedingt geringe, naturnahen DOC-Konzentrationen erreicht werden können. / Losses of dissolved organic carbon are of environmental concern, as DOC is a potential source of gaseous carbon emissions and harms drinking water quality. Lack of knowledge particularly exists for lowland fens. Therefore, the influence of land management and site characteristics on DOC was studied at a catchment and a lysimeter scale. A rewetted fen was investigated showing considerabely lower ditch DOC concentrations and slightly lower DOC losses as compared to an agriculturally used fen. The influence of water levels and vegetation was relatively small in lysimeter trials, while each fen soil seems to have a specific potential for DOC release due to its susbtrate quality and genesis.

<p>Bacteria and fungi dominate the decomposition of aquatic plants, a major process in the carbon and nutrient cycling in many aquatic systems. Although phylogenetically distant, bacteria and fungi often live in close proximity with each other. Since these microorganisms also have similar ecological functions, interactions have developed between them. This thesis explores the nature of such interactions, and the potential effects on key components of the decomposition process. The thesis includes a critical assessment of the ergosterol method for determination of fungal biomass, a survey of the environmental factors determining the distribution and taxa numbers of litter-decomposing bacteria and fungi in lakes, and a number of experiments on the interactions between bacteria and fungi. In all the experiments performed, fungi responded to bacterial presence through antagonism, although different fungal strains, bacterial communities and substrates were used. The antagonism seemed to be caused by interference competition for substrate. The fungal effect on bacteria was less consistent. Bacterial growth was suppressed, unaffected, or even enhanced by the presence of fungi. Fungi contributed more to extracellular enzyme production than bacteria, and bacteria were probably able to assimilate intermediate decomposition products formed through the activity of extracellular enzymes of fungal origin. Thus, the effect on bacteria from interacting with fungi was determined by the balance between competition and benefit from excreted enzymes. Bacteria and fungi also used different size fractions of the organic matter, according to their different enzymatic capacities. Hence, bacteria appeared to assimilate low-molecular-weight compounds, while high-molecular-weight compounds were utilized primarily by fungi. </p><p>In brief, the ecological interactions influenced the growth and hence also the biomass development of bacteria and fungi, which affected enzyme activity as well as utilization of dissolved organic matter. Therefore, I suggest that interactions between bacteria and fungi influence degradation of plant litter in aquatic systems.</p>

Bacteria and fungi dominate the decomposition of aquatic plants, a major process in the carbon and nutrient cycling in many aquatic systems. Although phylogenetically distant, bacteria and fungi often live in close proximity with each other. Since these microorganisms also have similar ecological functions, interactions have developed between them. This thesis explores the nature of such interactions, and the potential effects on key components of the decomposition process. The thesis includes a critical assessment of the ergosterol method for determination of fungal biomass, a survey of the environmental factors determining the distribution and taxa numbers of litter-decomposing bacteria and fungi in lakes, and a number of experiments on the interactions between bacteria and fungi. In all the experiments performed, fungi responded to bacterial presence through antagonism, although different fungal strains, bacterial communities and substrates were used. The antagonism seemed to be caused by interference competition for substrate. The fungal effect on bacteria was less consistent. Bacterial growth was suppressed, unaffected, or even enhanced by the presence of fungi. Fungi contributed more to extracellular enzyme production than bacteria, and bacteria were probably able to assimilate intermediate decomposition products formed through the activity of extracellular enzymes of fungal origin. Thus, the effect on bacteria from interacting with fungi was determined by the balance between competition and benefit from excreted enzymes. Bacteria and fungi also used different size fractions of the organic matter, according to their different enzymatic capacities. Hence, bacteria appeared to assimilate low-molecular-weight compounds, while high-molecular-weight compounds were utilized primarily by fungi. In brief, the ecological interactions influenced the growth and hence also the biomass development of bacteria and fungi, which affected enzyme activity as well as utilization of dissolved organic matter. Therefore, I suggest that interactions between bacteria and fungi influence degradation of plant litter in aquatic systems.

Ce travail a pour objectif principal l'étude des interactions entre les compartiments procaryotiques des zones méso- et bathypélagique avec les différentes fractions du carbone organique dissout (DOC) océanique. Des mesures d'assimilation de monomères (3H-Glucose), de dégradation de molécules complexes (3H-EPS et HMW-DOC), et de production hétérotrophe procaryotique (PHP/3H-Leucine) ont été réalisées le long de la colonne d'eau en Mer Méditerranée Nord Occidentale (Golfe du Lion, sites DYFAMED, ANTARES) et en Océan Atlantique Nord-Est (site PAP). Au cours des ces études, toutes les mesures réalisées au-delà de 1000 m de profondeur ont été effectuées dans des conditions in situ de haute pression hydrostatique (> à 10 MPa, HP) et comparées à des mesures réalisées sous pression atmosphérique (0,1 MPa, ATM). Cette double mesure détermine le rôle de la pression hydrostatique sur les activités microbiennes profondes via un rapport Pe pour pressure effect (= mesure HP / mesure ATM). Les résultats démontrent que les activités microbiennes mesurées en conditions HP sont plus importantes qu'en conditions ATM en période de stratification des eaux, (Pe moyen de 4,01, n=120), et confirment la capacité des procaryotes du domaine océanique profond à dégrader des molécules organiques complexes. Par ailleurs et à une échelle cellulaire, les populations métaboliquement actives du milieu profond dégradent les 3H-EPS à une vitesse 6 fois plus rapide que leur homologue de surface, indiquant la capacité des procaryotes autochtones profonds à dégrader des molécules plus complexes en conditions de haute pression. / This main objective of this work is the study of interactions between prokaryotic compartments of meso-and bathypelagic zones with different size classes of dissolved organic carbon (DOC). Several measurements of monomers assimilation (3H-Glucose), of complex molecules degradation (3H-EPS and HMW-DOC) and prokaryotic heterotrophic production were realized through the water column of NW Mediterranean Sea (Gulf of Lion, DYFAMED and ANTARES station) and NE Atlantic Ocean (PAP site). During these studies, all measurements realized below 1000 m depth, were carry out under in situ condition of hydrostatic pressure (> 10 MPa, HP) and compared to their decompressed counterpart measurements, realized at atmospheric pressure (0.1 MPa, ATM). These coupled measurements determine the role of hydrostatic pressure on deep sea microbial activity following the Pressure effect (Re) ration (=HP measurement / ATM measurement). The results show that microbial activities measured under HP condition during stratified water period, were more important than those measured under ATM condition (mean Pe = 4.01, n=120), and confirm the abilities of deep sea prokaryotes to degrade complex organic molecules. Moreover, the cell-specific activity of deep sea prokaryotes in 3H-EPS degradation are 6 time more active than the surface, indicating the ability of autochthonous deep sea prokaryotes to degrade complex molecules under high conditions of pressure.