Dissertations / Theses on the topic 'Dissolved organic carbon'

Peatlands are serving as one of the most important terrestrial carbon stores in the United Kingdom and globally. In the UK, the current trend of peatlands turning from carbon sinks to carbon sources is widely observed and reported. As numerous factors may affect the carbon cycle of peatlands, including climate, land management, hydrology and vegetation, dissolved organic carbon (DOC) was commonly used as an indicator of peatland carbon changes. Besides the function as an indicator of carbon turnover in peatland, increasing DOC in the stream water also raises concern in water companies as the removal of DOC from water represents a major cost of water treatment. This thesis investigates the impacts of land management such as drain blocking and revegetation on stream DOC changes. By building a pilot column study, this thesis also assessed the potential of bank filtration serving as DOC treatment in UK. Results of drain blocking shows the management was a significant impact on the DOC changes. However, later investigation of peak flow events indicates such positive impacts from drain blocking were minor in terms of high peak flow events. Since the majority of DOC export occurred during such peak flow events, drain blocking were found not as an efficient management of DOC changes. The field study of revegetation observed minor effects of revegetation on stream DOC. The results of column bank filtration indicate low DOC removal rate under the current stream DOC level in UK. The bank filtration may efficient remove DOC when higher DOC input applied. However, it is not suitable for UK peatland under current DOC export.

The marine biogeochemistry of dissolved organic carbon (DOC) has come under increased scrutiny because of its involvement in the global carbon cycle and consequently climate change. Dissolved organic nitrogen (DON) and phosphorus (DOP), which have historically been ignored because of their suggested “biological unavailability”, have now received greater attention due to their importance in nutrient cycling, particularly in oligotrophic ecosystems. DOM, a byproduct of photosynthetic production, has important ecological significance as a substrate that supports heterotrophic bacterial growth, thereby causing oxygen consumption and regenerating inorganic nutrients. In the open ocean the net production of DOC is ultimately due to the decoupling of biological production and consumption processes. Concentrations of DOM in the surface oceans, therefore, are controlled by both physical and biological processes. This research investigates the biological factors that control the distributions of DOC, DON and DOP in surface waters, the importance of DOC degradation to oxygen consumption, the importance of DON and DOP degradation to remineralised dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphorus (DIP), and the C:N:P stoichiometry of DOM pool in the Atlantic Ocean. Samples were collected on Atlantic Meridional Transects (AMT) cruise 16 and 17, which crossed the southern temperate region, the southern subtropical gyre, the equatorial region, the northern subtropical gyre, and the northern temperate region. This work described here was performed as a component of the AMT programme. Concentrations of DOC and TDN were determined using a high-temperature catalytic combustion technique, and TDP concentrations were determined using a UV oxidation method. Concentrations of DON and DOP were estimated as the difference between the independent measurements of TDN and TDP. The results showed that the highest DOM concentrations were found in surface (0-30 m) waters, ranging from 70-80 µM DOC, 4.8-6.5 µM DON and 0.2-0.3 µM DOP, and decreased with increasing water depth to 45-55 µM DOC, 2.6-4.0 µM DON and 0.04-0.05 µM DOP at 300 m. The lowest DOM concentrations were observed in the deep (>1000 m) ocean, averaging 44 µM DOC, 2.3 µM DON and 0.02 µM DOP. In the upper 300 m, the concentrations of semilabile (and labile) DOC decreased by 45-95% from the surface values. DON and DOP were the dominant components of the total dissolved nutrient pools in the upper 50 m, accounting for up to 99% and 80% of the TDN and TDP pools, respectively. In the upper 300 m, semilabile (and labile) DON and DOP decreased by 50-65% and 90-95% from the surface values, respectively. The decoupled correlations between DOC/DON/DOP and chlorophyll-a and rates of carbon fixation suggested that phytoplankton biomass and rates of primary production were not the important controls of the cumulative DOC, DON and DOP. Zooplankton grazing was hypothesised to be an important factor in regulating the distributions of DOC, DON and DOP in surface waters. Poor correlations between DOC/DON/DOP and DIN/DIP suggested that inorganic nutrients were not the significant controls in DOC, DON and DOP distributions. N and P were probably retained mainly in the organic pool in the surface waters due to a hypothesised insufficient functioning of the microbial degradation. If the vertical migration of zooplankton was significant in bringing new nutrients into the surface waters, strong correlations between dissolved organic and inorganic nutrients should not be anticipated. Prochlorococcus spp. abundance was statistically linked with the concentrations of DOC, DON and DOP. The significant correlations may reflect the ability of Prochlorococcus to assimilate the labile forms of dissolved organic nutrients (including DOC), which may be quantitatively significant in surface waters of the Atlantic Ocean. The C:N, N:P and C:P stoichiometry of the bulk DOM pool deviated from the Redfield ratio of 6:1, 16:1 and 106:1, ranging from 12-18, 20-100 and 300-1400, respectively, in the upper 300 m, suggesting that the cumulative DOM was rich in C relative to N and P, and N relative to P compared to the Redfield trajectories. The offsets of the C:N:P stoichiometry relatively to the Redfield ratio were due to nutrient limitations that imposed on prokaryotic and eukaryotic microbial populations. The C:N:P stoichiometry of the bulk DOM pool showed an increased trend, with C:N = 12-16, N:P = 20-25, and C:P = 300-350 in the upper 30 m, C:N = 12-18, N:P = 50-100, and C:P = 700-1400 at 300 m, and C:N = 17-24, N:P = 79-132; C:P = 1791-2442 at 1000 m. The differences in the C:N:P stoichiometry of the bulk DOM pool between the upper and deep waters suggested preferential remineralisation of P relative to C and N, and N relative to C. A greater remineralisation length scale for DOC relative to DON and DOP produced a long-term, steady flux of C from the surface to the deep ocean. Therefore, CO2 fixed in the upper ocean during planktonic photosynthesis was continuously “pumped” into the ocean interior, and stored in the deep ocean up to thousands of years. The C:N, N:P and C:P stoichiometry of the semilabile (and labile) DOM pool generally agreed with the Redfield ratio (C:N = 6; N:P = 16; C:P = 106) in the upper 30 m. At 100 m C:N ratio was 5-12, C:P ratio was 20-30, and C:P ratio was 100-150. At 300 m, C:N ratio was 5-12, N:P ratio was 25-100, and C:P ratio was 150-500. The findings suggested that in the upper 300 m, there was no preferential remineralisation between the semilabile (and labile) DOC and DON, however, the semilabile (and labile) DOP seemed to be preferentially remineralised relative to the semilabile (and labile) DOC and DON. In the upper thermocline (i.e. above 300 m), DOC degradation was important with respect to oxygen consumption, contributing to as much as 25% of the apparent oxygen utilization (AOU). The remaining of 75% was attributable to POC decomposition. However, the AOU contributable to DOC showed a function of latitude, with 15-55% found in the central subtropical Atlantic gyres and 15-25% in the equatorial region. The most likely explanation for the variation of DOC relative to POC degradation with respect to AOU was the regional variability in the export of POC, which was suggested to be highest in the high nutrient regions of the equator and at the poleward margins of the subtropical gyres. As a result, DOC formed an important contribution to AOU in oligotrophic regions, while POC was the dominant control of AOU in upwelling regions. Some freshly-produced fractions of DON and DOP with turnover times of months to years were capable of escaping rapid microbial degradation in surface waters and became entrained into deep waters via diffusive mixing. Subsequent microbial degradation of these DON and DOP took place in the thermocline, regenerating inorganic nutrients. Statistically significant correlations were observed between the DON-to-DIN and DOP-to-DIP relationships. Calculations of the fluxes of dissolved organic nutrients relative to inorganic nutrients suggested that in the upper thermocline (i.e. above 300 m), the downward fluxes of DON and DOP contributed to a total of 4% and 5% of the upward fluxes of DIN and DIP, respectively, into the euphotic zone. The remaining of 95% of the upward dissolved inorganic nutrients fell out of the euphotic zone as particles in order to prevent nutrient accumulation and to maintain nutrient integrity of the pelagic ecosystem.

Streams and rivers are an integral component of the freshwater carbon cycle as they provide the lateral transport of carbon from terrestrial environments to the ocean. Urbanization is one of the fastest growing land uses and it has major impacts on streams and rivers. This study examined twenty-eight watersheds varying in land uses from pre-restoration forested to urban in Charlotte, North Carolina. Their impervious cover ranged from 0.5–55%. The objective of this study was to examine alterations to freshwater carbon processes among watersheds of various land uses in multiple streams in Mecklenburg County, Charlotte, NC.

Surface water was collected at each site in addition to discharge measurements. Water quality parameters were analyzed including: DOC concentration, Specific UV Absorbance of DOC, DIC concentration, alkalinity concentration, δ ¹³C-DIC, major cations (Na⁺, K⁺, Mg ²⁺, and Ca²⁺), and anions (F^–, Cl^–, PO₄^3–, NO ^3–and SO₄^2–). DOC concentration ranged from 1.1–18 mg/L and SUVA values ranged from 0.2–18 L/mg*m. Alkalinity concentrations ranged from 0.1–3.8 meq/L and DIC concentrations ranged from 0.2–3.8 mM. δ¹³C-DIC values ranged from –18.0‰ to –7.4‰. Overall, DOC concentrations and SUVA values had weak negative relationships with percent impervious cover. DIC concentrations, alkalinity concentrations, δ¹³C-DIC values, all cations, and F^–, Cl^– , and SO₄^2– had strong positive relationships with percent impervious cover. PO₄^3– and NO ^3– had weak correlations with percent impervious cover. The increase in DIC, alkalinity, δ¹³C-DIC, and cations with high impervious cover was largely due to the increased chemical weathering of concrete materials in urban areas.

Dissolved organic matter (DOM) including carbon and nitrogen (DOC and DON) are important but poorly understood components of the marine biogeochemical cycle. In this study, the distribution and cycling of DOC and DON, and particulate organic carbon and nitrogen (POC and PON) were investigated in North Sea surface and bottom water during the stratified summer season in 2011 and 2012, along with other key biogeochemical parameters such as nutrients. The summer DOC, DON, POC and PON ranged from 32.7-134.5, 2.8-13.7, 1.1-43.8 and 0.3-5.9 μM, respectively. The well-mixed water of the southern North Sea was also surveyed in the winter of 2011; measured concentration of DOC and DON were 56.2-224.8 and 3.7-12.3 μM. In summer, DOM and POM generally exhibited high levels in the southern well-mixed water (SM), whereas inorganic nutrient concentrations were higher in the northern bottom water (NB) due to nutrient regeneration and offshore water inflow. DOM in summer and inorganic nutrients in winter were also clearly influenced by riverine inputs. DON was the dominant nitrogen fraction of northern surface water and SM in summer, while in NB, TOxN (nitrate + nitrite) was the dominant fraction. Analysis of SmartBuoy samples show phytoplankton provided a net source of DOM over the spring bloom period with net degradation in autumn and winter. Incubation experiments on water collected from two North Sea sites in autumn, winter 2013 and spring 2014 showed no nutrient (N and P) limitation on DOM degradation. The experiments yield mean bacterial decay rate constants (for three seasons) at the two sites of 4 ± 8 and 2 ± 3 %d-1 kDOC and 3 ± 4 and 4 ± 4 %d-1 kDON, under dark conditions. In comparison to the Redfield ratio, the bulk C:N molar ratio is enriched in carbon relative to nitrogen, while the slope C:N ratio is close to the Redfield ratio, but with a background of high C:N material.

The contribution of dissolved organic carbon (DOC) to mineral weathering was investigated under the changing Eh and pH conditions in three subarctic fens, near Schefferville, Quebec. No evidence of increased weathering rates nor different weathering patterns were found in the fen basal sediment despite DOC-rich and low Eh (0 to +200 mV) conditions.
Solutions containing 50 mg DOC/L derived from subarctic fen peat, and of 50 and 300 mg DOC/L, derived from deciduous leaf litter were used as weathering agents. Clinochlore, microcline and the Fe-rich basal till from the Schefferville fens were used as weatherable mediums. The DOC rich solutions and controls (made of distilled water buffered to the same initial pH) were used to investigate the relative weathering ability of DOC-rich waters under aerobic and anaerobic conditions. The relative ability was determined by comparing the changing cation concentrations in the solutions.

Carbon-14 was measured in the dissolved organic carbon (DOC) in ground water and compared with ¹⁴C analyses of dissolved inorganic carbon (DIC). Two field sites were used for this study; the Stripa mine in central Sweden, and the Milk River Aquifer in southern Alberta, Canada. The Stripa mine consists of a Precambrian granite dominated by fracture flow, while the Milk River Aquifer is a Cretaceous sandstone aquifer characterized by porous flow. At both field sites, ¹⁴C analyses of the DOC provide additional information on the ground-water age. At the Stripa site the DIC from the recharge area probably precipitates at around the 300 m level of the mine, never reaching the deeper ground waters. In this case, ¹⁴C analyses of the DOC provides a better estimate of the ground-water age. The dilution of the DIC by carbonates and microbial processes in the Milk River Aquifer is so great that geochemical corrections of ¹⁴C data are difficult. This is another example where ¹⁴C analyses of the DOC provide more information on ground-water age. Carbon-14 was measured on both the hydrophobic and hydrophilic organic fractions of the DOC. At the Stripa site, the hydrophobic organic compounds in the V2 borehole ranged from 7,500 to 15,500 years before present, suggesting a young component of ground water. Other hydraulic and isotopic evidence supports relatively recent ground water mixing with older brines in this borehole. The δ¹³C values of the DIC in the V2 borehole are light and similar to the stable carbon isotope values for the DOC, supporting a biogenic origin of the DIC. The organic compounds in the hydrophobic and hydrophilic fractions were also characterized. The DOC may originate from kerogen in the aquifer matrix, from soil organic matter in the recharge zone, or from a combination of these two sources. Carbon-14 analyses, along with characterization of the organics, were used to determine this origin. Carbon-14 analyses of the hydrophobic fraction in the Milk River Aquifer suggest a soil origin, while ¹⁴C analyses of the hydrophilic fraction suggest an origin within the Cretaceous sediments (kerogen) or from the shale in contact with the aquifer.

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.

Blue carbon systems (mangroves, salt marshes, and seagrass beds) sequester large amounts of carbon via primary productivity and sedimentation. Sequestered carbon can be respired back to the atmosphere, buried for long time periods, or exported (“outwelled”) to adjacent ecosystems. This study estimates the total outwelling of dissolved organic carbon (DOC) from the Neponset Salt Marsh (Boston, Massachusetts) as well as the major plant and sediment processes contributing to the overall flux. The total export was quantified via high-resolution in situ chromophoric dissolved organic matter (CDOM) measurements as a proxy for DOC using 12 years of transect data. Seasonal trends, alternate sources of fresh water, and long-term trends in DOC export will be discussed. To characterize the percentage of this flux attributable to marsh vegetation, the effects of sunlight, anoxia, plant species, biomass type, and microbes on plant leaching were studied using incubations of above- and belowground biomass over four seasons. Seasonal comparisons led to the “Fall Dump” hypothesis in which higher DOC concentrations are leached during the fall when marsh plants senesce for winter. In summing seasonal fluxes from vegetation, approximately 46% of the total DOC export from the marsh may be attributed to leaching from the three dominant plant species in the Neponset Salt Marsh. The influence of seasonality and climate change (e.g., drought) on both overland flow and deep sediment pore water leaching were also investigated. Depending on season and marsh condition, overland flow and sediment pore water leaching combined could contribute 8–16% of the total export from the marsh. Finally, the influence of natural sunlight irradiation and microbes on the release of dissolved organic matter (DOM) from resuspended surface sediments was studied and approximately 11–22% of the total export could be attributable to this flux. Approximately 49 mol C m⁻² yr⁻¹ are outwelled from the Neponset Salt Marsh and, using net primary productivity estimates from the literature, 16 ± 12 mol C m ⁻² yr⁻¹ are buried in the Neponset Salt Marsh.

The aim of this thesis was to investigate soil and environmental factors which influence the adsorption of DOC in upland, moorland soils. In Chapter 1 climate change, the greenhouse effect and the global carbon cycle are discussed briefly. A more detailed discussion of carbon cycling in the plant-soil-water system focuses on DOC retention in podzols and the review concludes with a summary of the aims of this thesis. A peaty podzol has greater potential to retain DOC than the other major soil types within the Glen Dye catchment, N.E. Scotland. Retention of DOC by physico-chemical surface interactions occurred in the mineral horizons of the soil where locally high concentrations of amorphous Fe and Al were present. Laboratory experiments using potassium hydrogen phthalate as a source of DOC showed that DOC retention is favoured by longer contact times between soil and solution. Net retention of DOC in the podzol profile is decreased by increasing the solution pH and by repeated wetting/drying and freezing/thawing cycles. As temperature and reaction time increased, respiration becomes more important as a mechanism for depleting solution phthalate DOC concentrations. Annual fluxes of DOC in precipitation, podzolic O, E and Bs soil horizon solution and stream water were estimated for the Burn of Waterhead catchment to be 35, 121, 83, 37 and 48 kg C ha-1yr-1 respectively. The DOC fluxes and the concentrations of related elements varied seasonally, with the largest DOC fluxes produced in the autumn and lowest in the summer. The annual DOC flux from the Burn of Waterhead was lower than fluxes from other catchments at Glen Dye. Results from the field site supported laboratory experimental results which suggested that climate change will result in an increase in the DOC flux from results which suggested that climate change will result in an increase in the DOC flux from peaty podzolic soil.

The presence of natural dissolved organic carbon (DOC) in drinking water supplies is undesirable due to its reaction with chlorine during water treatment and the resulting formation of disinfection by-products (DBPs) (Rook, 1976). Some of these compounds, principally trihalomethanes (THMs), have demonstrated carcinogenic properties and can potentially cause damage to the reproductive system (Bull, et al, 1995; Nieuwenhuijsen, et al, 2000). Concentrations of DOC in freshwater rivers and lakes in the UK have increased by 91% during the last 15 years (Evans, et aL 2005), with the rise attributed to the destabilisation of peatland soils through climate change, and the release of some of the vast carbon store of 455 Pg they have accumulated over the last few thousand years (Gorham, 1991). If the increase continues, it will create a serious challenge to water companies due to the need to minimise the formation of harmful DBP compounds. This project investigated the role of peatlands in the formation of THMs at selected reservoirs in north Wales. Water draining from Cors Erddreiniog fen into Cefni reservoir was found to be the most important source of DOC, comprising 33-57% of all the inputs to the lake on an annual basis; however, it was also demonstrated that sunlight can strongly degrade the DOC entering the lake from this source, thereby reducing its THMforming potential. Rapid growth of algae during the summer months contributes up to 45% of all the DOC inputs, although the lower molecular weight of the carbon compounds ensures that algae do not generate THMs as readily as terrestrially-derived DOC during water treatment. At Marchlyn Bach and Llugwy reservoirs, the DOC concentration of the lake water was lower, due to both the bog soils within the catchment releasing less DOC than the fen, and the much lower autochthonous production. The impact of rising temperatures on peat soil was to increase the leachability of DOC during spring for bogs and summer for fens, the latter being important for the Cefni as this is when THM concentrations are highest. Exposure to elevated concentrations of atmospheric ozone reduced the porewater DOC concentration of fen peat by as much as 55%, suggesting that through its effects on the carbon allocation within the above ground vegetation, elevated ozone could partially offset the predicted increasei n DOC leaching from fen ecosystemsth rough enhancedw arming and C02 concentrations.

Stream ecosystems form an active component of the carbon (C) cycle, and are identified as “hotspots†for carbon dioxide (CO2) emissions. However, the mechanisms driving CO2 emissions from streams are not completely understood. Beside the input of C in the form of CO2 from groundwater, streams receive organic matter from aquatic and terrestrial origins which is partly mineralized to inorganic nutrients and CO2. Future predictions suggest enhanced input of terrestrial organic matter into streams. As such, surrounding land use may highly influence dissolved organic matter (DOM) composition and turnover in streams. The quality, i.e. bioavailability or lability, of aquatic and terrestrial organic matter, as well as which quality feature provides which bioavailability, is controversially discussed and the research is still in its infancy. Thus, the main goal of my thesis is to enhance the understanding of the role of organic matter quality as a potential driver for organic matter turnover in stream ecosystems. A further goal is to shed light on C dynamics with main focus on CO2 of streams surrounded by different land use. The presented work is based on an experimental approach in the laboratory, supported by seasonal field studies and a developed model in order to explore C dynamics and the corresponding drivers in stream ecosystems. The underlying mechanisms and the importance of DOM quality as a main driver was assessed on the small scale in laboratory experiments. The C emissions from streams were quantified and the influence of DOM quality was examined on a stream reach scale by investigating two stream types with different organic matter quality inputs. By developing a process-based model, the understanding of the daily and seasonal scale of C turnover in stream ecosystems was amplified. The results from the experiment under controlled conditions demonstrate that DOM quality governs microbial metabolism (i.e. respiration and bacterial protein production). Moreover, I revealed significant quality differences between two terrestrial DOM sources, while respiration and bacterial protein production increased with the available proportion of the labile DOM source. The molecular weight of DOM was the strongest predictor of bacterial protein production and respiration, while among others, the concentration of low molecular weight substances was another highly influential predictor. The importance of molecular size/weight and DOM quality for microbial metabolism was further confirmed on the stream reach scale where we demonstrated among others a significant linkage between molecular size of DOM and pCO2 across agricultural and forest streams. Moreover, agricultural streams contained significantly higher pCO2 compared to forest streams during all seasons. However, CO2 emissions measured with the powerful drifting chamber method were not significantly different between the stream types. Modeled dissolved oxygen (O2) and CO2 dynamics calibrated with field data resulted in respiratory quotients (RQ = mole of CO2 produced per mole of O2 consumed), which are intimately linked to the elemental composition of the respired compounds across four seasons and two stream types. RQ values were not related to adjacent land use or season. Nevertheless, I found significant relationships between RQ values and DOM quality indicators, such as fluorescing component characteristic for higher plant material and molecule size of DOM in agricultural streams. In conclusion, this thesis demonstrates that DOM quality is an important driver for organic matter turnover in streams. Consequently, my results indicate that ongoing and future land use change and enhanced terrestrial DOM input into streams may influence CO2 emissions, and underline the status of streams as C turnover “hotspots†. Thus, my thesis contributes to the mechanistic understanding of organic matter cycling in stream ecosystems and their role in the regional and global C cycle. Therefore, organic matter quality should be considered in future models and studies with respect to C cycling.

Stream ecosystems form an active component of the carbon (C) cycle, and are identified as “hotspots” for carbon dioxide (CO2) emissions. However, the mechanisms driving CO2 emissions from streams are not completely understood. Beside the input of C in the form of CO2 from groundwater, streams receive organic matter from aquatic and terrestrial origins which is partly mineralized to inorganic nutrients and CO2. Future predictions suggest enhanced input of terrestrial organic matter into streams. As such, surrounding land use may highly influence dissolved organic matter (DOM) composition and turnover in streams. The quality, i.e. bioavailability or lability, of aquatic and terrestrial organic matter, as well as which quality feature provides which bioavailability, is controversially discussed and the research is still in its infancy. Thus, the main goal of my thesis is to enhance the understanding of the role of organic matter quality as a potential driver for organic matter turnover in stream ecosystems. A further goal is to shed light on C dynamics with main focus on CO2 of streams surrounded by different land use. The presented work is based on an experimental approach in the laboratory, supported by seasonal field studies and a developed model in order to explore C dynamics and the corresponding drivers in stream ecosystems. The underlying mechanisms and the importance of DOM quality as a main driver was assessed on the small scale in laboratory experiments. The C emissions from streams were quantified and the influence of DOM quality was examined on a stream reach scale by investigating two stream types with different organic matter quality inputs. By developing a process-based model, the understanding of the daily and seasonal scale of C turnover in stream ecosystems was amplified. The results from the experiment under controlled conditions demonstrate that DOM quality governs microbial metabolism (i.e. respiration and bacterial protein production). Moreover, I revealed significant quality differences between two terrestrial DOM sources, while respiration and bacterial protein production increased with the available proportion of the labile DOM source. The molecular weight of DOM was the strongest predictor of bacterial protein production and respiration, while among others, the concentration of low molecular weight substances was another highly influential predictor. The importance of molecular size/weight and DOM quality for microbial metabolism was further confirmed on the stream reach scale where we demonstrated among others a significant linkage between molecular size of DOM and pCO2 across agricultural and forest streams. Moreover, agricultural streams contained significantly higher pCO2 compared to forest streams during all seasons. However, CO2 emissions measured with the powerful drifting chamber method were not significantly different between the stream types. Modeled dissolved oxygen (O2) and CO2 dynamics calibrated with field data resulted in respiratory quotients (RQ = mole of CO2 produced per mole of O2 consumed), which are intimately linked to the elemental composition of the respired compounds across four seasons and two stream types. RQ values were not related to adjacent land use or season. Nevertheless, I found significant relationships between RQ values and DOM quality indicators, such as fluorescing component characteristic for higher plant material and molecule size of DOM in agricultural streams. In conclusion, this thesis demonstrates that DOM quality is an important driver for organic matter turnover in streams. Consequently, my results indicate that ongoing and future land use change and enhanced terrestrial DOM input into streams may influence CO2 emissions, and underline the status of streams as C turnover “hotspots”. Thus, my thesis contributes to the mechanistic understanding of organic matter cycling in stream ecosystems and their role in the regional and global C cycle. Therefore, organic matter quality should be considered in future models and studies with respect to C cycling.

The sources, sinks, fluxes, spatial distributions, and temporal variations of dissolved organic carbon (DOC) in subarctic fen catchments as well as the temporal patterns of DOC in streams draining subarctic fen catchments in the region of Schefferville, Quebec were investigated.
In June to August sampling, DOC concentrations averaged 17 mg/L in peat water, 2-16 m/L in stream water, 49-56 mg/L in canopy throughfall, 14-19 mg/L in understory throughfall, 122-187 mg/L in stemflow, 25-39 mg/L in lichen and moss mat water, and 35-42 mg/L in soil A horizon water.
Precipitation and canopy and understory throughfall were all significant DOC sources with seasonal DOC fluxes to the forest floor of 0.1-0.4, 0.5-1.3, and 0.8-1.7 g DOC/m$ sp2$ of forest, respectively. The lichen and moss mats and the A soil horizon were also found to be DOC sources, whereas the B soil horizon was a DOC sink. The soil column was estimated to export 0.4-0.5 g DOC/m$ sp2$. Peat, also a DOC source, released 1.2-2.1 g DOC/m$ sp2$.
DOC concentrations in streams draining ten fen catchments were found to be positively correlated with the percentage of fen area in the catchments.

Snowmelt river systems exhibit seasonal fluxes in water chemistry, potentially affecting the water supply of one-sixth of the world<'>s 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<&hyphen>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.

Surface waters receive large amounts of dissolved organic matter (DOM) via runoff from land. The DOM is rich in organic carbon that serves as an energy source for the aquatic biota. During uptake of this energy, aquatic organisms mineralize organic carbon. The resulting inorganic carbon is partially released to the atmosphere as carbon dioxide and methane that are greenhouse gases, and which are of concern for the ongoing global warming. The rate at which organic carbon is mineralized depends strongly on DOM quantity and quality that vary with respect to both time and space. In this thesis, DOM quantity and quality were addressed using spectroscopic methods that build on the absorptive and fluorescent properties of chromophoric DOM (CDOM). New techniques to measure CDOM absorption and fluorescence were applied and further developed that allowed us to present novel CDOM variability patterns. Addressing the lake-rich Scandinavian landscape, strong focus was placed on water retention by lakes that tightly links to lake DOM quantity and quality. An analysis of 24,742 lakes from seven large Swedish river systems indicated that the majority of lakes in Sweden exchange their water within one year. From headwaters to the Sea, summed lake volumes in the catchments of lakes were found to increase at rates comparable to discharge, which indicated effective water renewal along flow. A strong relationship between lake water retention and CDOM was apparent and further investigated based on samples from a lake district to a regional scale. Results from in situ high-frequency monitoring of CDOM absorption in a eutrophic humic lake showed intra-annual variability patterns known from oligotrophic lake systems. The patterns for CDOM absorption contrasted results obtained for synchronously measured partial pressures of carbon dioxide that showed diurnal signals. Measurements of CDOM fluorescence and DOC concentrations indicated lake-internal DOM production. A comparison of these results with results from addressing 560 lakes distributed across Sweden, showed that a well-calibrated CDOM fluorescence measurement captures signals from lake-internal DOM production. I conclude that improved CDOM fluorescence measurements are promising to address lake-internally produced DOM.

Soils in permafrost regions hold substantial amounts of carbon, much of which has accumulated due to processes that are related to cold temperatures. A warming climate will alter the dynamics governing the fluxes of carbon within a system and consequently the pools of carbon therein. Of particular concern is whether previously stored carbon will be released to the atmosphere contributing to the pool of greenhouse gases and creating a feedback effect. At the moment the International Panel of Climate Change (IPCC) does not include carbon dynamics of the Arctic in their forecast models due to a lack of adequate scientific understanding in the area. Understanding the controls which govern the fluxes of carbon between the land, the atmosphere and the aquatic systems is important in evaluating the transient state of the carbon cycle. This study investigates the potential relationship between terrestrial soil organic carbon (SOC) pools and the dissolved organic carbon (DOC) concentrations in streams observed at the beginning of August 2012 in the Abiskojokka catchment in the sub-arctic region of northern Sweden. The results show that soil organic carbon pools could tentatively explain between 24 % and 44 % of the variation in DOC concentrations in streams. This is only a fraction of the variation explained compared to regions where peatlands are the single most important indicator of DOC concentrations. In the absence of peatland, which covers less than 2 % of the Abiskojokka catchment area, heath vegetation and the associated soil forming processes were shown to be an important indicator of stream water DOC concentrations.

In river networks, dissolved organic matter (DOM) constitutes the major pool of organic carbon, and plays a key role as energy source and modulator of toxic substances availability. In this thesis, Joan P. Casas-Ruiz and collaborators provide new insights into the controls on DOM processing, and into how in-stream reactions and changing DOM sources modulate DOM dynamics in river networks. To attain this, the quantity and composition of DOM were evaluated across a river network throughout a full hydrological year. The results compiled in this thesis pose water residence time as the main regulator of DOM processing, while DOM properties as well as nutrient availability determine the net balance of in-stream degradation and production of DOM. A network-scale analysis identifies a pattern of DOM concentration and chemical diversity with maxima in medium-sized rivers, and the same pattern emerges upon analysis of a global data set. On the basis of these results, this thesis proposes a conceptual framework to comprehend and predict the spatiotemporal dynamics of riverine DOM
La matèria orgànica dissolta (DOM) constitueix la major reserva de carboni orgànic en els sistemes fluvials, on també hi juga un paper clau com a font d'energia i modulador de la disponibilitat de substàncies tòxiques. En aquesta tesi, Joan P. Cases-Ruiz i col•laboradors pretenen identificar els controls de processament DOM, i entendre com la combinació de reaccions in situ i canvis en les fonts de DOM modulen les dinàmiques de la DOM fluvial. Per tal d'assolir-ho, es van evaluar la quantitat i composició de la DOM en una xarxa fluvial al llarg d'un any hidrològic complet. Els resultats recopilats en aquesta tesi assenyalen el temps de residència de l'aigua com el principal regulador de processament de la DOM, mentre que les propietats intrínsiques de la DOM, així com la disponibilitat de nutrients determinen el balanç net de degradació i producció de la DOM. Una anàlisi a escala de xarxa fluvial identifica un patró de concentració i diversitat química de la DOM amb màxims en els rius de mida mitjana. En base a aquests resultats, aquesta tesi proposa un marc conceptual per comprendre i predir les dinàmiques espacials i temporals de la DOM fluvial

Denna avhandling behandlar den småskaliga rumsliga variationen av löst organiskt kol (DOC, engelsk term: dissolved organic carbon), dess koncentration, masstransport och karaktär, i bäckar inom två barrskogsbeklädda avrinningsområden (delavrinningsområden 0,01-78 km²). Provtagningen gjordes uppströms och nedströms varje bäckförgrening under sommarbasflöde. Koncentrationen av DOC varierade inom en tiopotens (4-66 mg/l), liksom flera andra kemiska parametrar. Vid riksinventeringen av vattendrag för 2000 i norra Sverige noterades en snarlik spännvidd. Enligt Naturvårdverkets bedömningsgrunder för sjöar och vattendrag återfanns alla tillståndsklasser för DOC och pH, samt mänsklig påverkansgrad till försurningen inom de två studerade områdena. Den specifika avrinningen (flöde per areaenhet) varierade kraftigt i källflödena och inverkade på deras bidrag till kemin nedströms. Vattenkemin och specifika avrinningen var stabila i delavrinningsområden större än 15 km². Det kan vara nödvändigt att provta så stora områden om generella värden för landskapet önskas, men källflödenas kemi kommer då inte att kunna karakteriseras, ehuru källflödena utgör den största delen av bäcksträckan och det akvatiska ekosystemet.

Nedströms är DOC-koncentrationen, och många andra kemiska parametrar, lika med summan av bidragen från källflödena och nedströms utspädning av inflödande vatten. Tillkommer gör processer inom bäcken och vattnets utbyte med botten/grundvatten (den hyporheiska zonen), men även DOC-förluster/transformationer vid vissa bäckförgreningar och sjöar. Ovanstående resonemang förklarade bäckvattenkemins minskande variation och vanligen lägre DOC-koncentrationer nedströms i ett landskapsperspektiv. Längs bäcksträckorna observerades ingen generell minskning av DOC-koncentration eller ändring av dess karaktär. Skillnaden i DOC-koncentration och relaterade parametrar mellan källflöden och nedströms styrdes i hög grad av vilka landskapselement (myrar, sjöar och skogsmark) som vattnet hade passerat innan det hamnade i bäckarna, samt samspelseffekter med den specifik avrinningen och platserna med DOC-förlust. Prognoser med multivariata modeller baserade på kartinformation testades men kunde inte förutsäga det rumsliga mönstret eller DOC-koncentrationen med erforderlig precision.

Lämpliga rutiner inom miljöövervakningen för att övervaka den rumsliga variationen av kemin i ytvatten saknas alltjämt. Vid planering av terrestra och akvatiska skötselåtgärder bör man beakta bäckvattnets naturliga kemiska variation.

This thesis quantifies the small-scale spatial variation of dissolved organic carbon (DOC) concentrations, fluxes and character in two boreal catchments (subcatchments 0.01-78 km²) using ”snapshots” of summer base flow where samples were taken upstream and downstream from every node in the stream network. An order of magnitude variation was found in DOC-concentrations, and many other chemical parameters. The range was similar to that found in all of northern Sweden by the national stream survey in 2000. According to the official assessment tools used in Sweden, the entire range of environmental status for DOC, pH and human acidification influence existed within these two study catchments. A large variability in specific discharge had a major impact on the contribution of headwaters to downstream chemistry. The water chemistry parameters were relatively stable at catchment areas greater than 15 km². Sampling at that scale may be adequate if generalised values for the landscape are desired. However the chemistry of headwaters, where much of the stream length and aquatic ecosystem is found would not be characterized.

Downstream DOC-concentrations, as well as many other chemical parameters, are the sum of headwater inputs, in combination with progressive downstream dilution by inflowing water with its own DOC-concentration and character. Superimposed upon this are in-stream and hyporheic processes, as well as discrete loci of DOC loss/transformation at lakes and stream junctions. At the landscape scale, this results in a decreased downstream variation in stream water chemistry and often, but not necessarily, lower average DOC-concentrations. Along stream reaches there was not a loss of DOC-concentration or a consistent change in character. While the importance of in-stream/hyporheic processes that consistently alter DOC-concentrations along the channel network cannot be ruled out, the differences between headwater and downstream DOC-concentrations and related parameters depend largely on the mosaic of landscape elements (mires, lakes and forest soil) contributing water to the channel network, combined with patterns of specific discharge and discrete loci of DOC loss. Assessment would be facilitated by map information that could predict spatial patterns. Multivariate models using maps, however, did not give satisfactory predictions.

Appropriate procedures for dealing with spatial variation in the environmental assessment of surface waters are not yet established. An awareness of stream water chemistry’s natural spatial variability should be considered when planning aquatic and terrestrial management.

A hydrological and biogeochemical study was undertaken at the Mer Bleue bog, Ottawa, Ontario, Canada from May 22, 1998 to May 21, 1999. Basin runoff was generated by groundwater discharge at the peatland margin, and groundwater discharge was controlled by hydraulic gradients and horizontal hydraulic conductivities (Kh). Flux of dissolved organic carbon (DOC) measured at the basin outflow was 8.3 g C m-2 yr-1 and compared to within 23% of DOC flux estimated using a Dupuit approximation of seepage during the ice-free season. Annual DOC flux was 11% of the annual carbon sink.
Flownet analysis showed that seasonal patterns of groundwater flow were controlled by boundary condition changes that resulted from precipitation and evapotranspiration events. A pattern of recharge was most common over the hydrological year, but a discharge pattern was observed during a 40 day groundwater flow reversal. Evaluation of the peatland recharge-discharge function using in situ sodium concentrations and a diffusion model revealed that the peatland is a long-term recharge system. It is hypothesized that peatland biogeochemical function is controlled by long-term recharge despite annual occurrence of groundwater flow reversals.

Biofouling, or the formation of biofilm on membrane surfaces, can decrease the performance (decreased flux and/or increased operating pressure) of a reverse osmosis (RO) membrane system in a water treatment plant. However, biofilms have been used in water treatment systems to remove organic carbon from water via biofilters and successfully reduce biofilm growth downstream. This research investigates the possibility that the heterotrophic biofilm present on membrane surfaces removes nutrients from the treatment water, thereby making it nutrient deprived as it travels along the treatment train. This may potentially be exploited as an in situ biofilter to actively remove dissolved organic carbon (DOC) from the treatment water, thereby protecting downstream membrane surfaces from biofouling. Analysis of fouled membranes from the Dunedin water treatment plant in Dunedin, FL indicates the presence of biofilm on membrane surfaces in a gradient pattern with a higher level of fouling at the front of the element. Additionally, the community structure of the biofilm at the front of the element is unique with respect to the feed-water and downstream membrane material. Additionally, a carbon (and nitrogen) mass balance study was performed at the water treatment plant in Dunedin, FL through extensive sampling of DOC at multiple locations of the RO membrane system over a 20 month period. Plant-level mass balance results indicate a significant pool of DOC was consistently unaccounted for, and presumably assimilated or otherwise removed within the membrane system. Sampling also indicated a removal of total nitrogen. Additionally, the specific UV absorbance (SUVA) of the DOC in concentrate was consistently greater than that of the feed water, suggesting the removal of labile aliphatic carbon as the feed water travels through the feed channel of the membrane system. A pilot system was designed and built to operate under plant conditions (flow rate and pressure) to test if the biofilm on the surface of the membrane can have a protective effect for downstream membrane material. A fouled membrane element was pulled from the plant at the same time and general location as an autopsied element (to determine composition on the surface) and used in the pilot system. Feed and concentrate water from the pilot was directed to flat sheet modules for performance testing and surface characterization. This allowed for characterization of the two sections without disturbing the membrane element. Differences in performance and foulant deposition were characterized for the two sections as a function of carbon addition and flow rate. The results from this testing suggest the membrane element, or the biofilm on its surface, has both a performance and a foulant deposition benefit for downstream membranes as compared to feed membrane material. This benefit also displayed an increasing trend as the concentration of organic carbon fed into the system increases.

Peatlands are important terrestrial stores of carbon and a principal source of dissolved organic carbon (DOC) to the fluvial environment. Whilst often regarded as a net carbon sink, enhanced DOC concentrations and an associated rise in the level of water discolouration observed in many artificially drained peatland catchments across Europe and North America suggests that continued degradation may shift the balance of the carbon budget, such that they become a net carbon source. Peatland restoration, in the form of drain blocking, is currently being undertaken in a number of these locations. However, a great deal of this work has been carried out on a pragmatic or even an ad-hoc basis, with a distinct lack of process-baseda ssessmentT. hus, very little is known about how such changes in land management affect DOC and colour dynamics. In order to bridge this knowledge gap, this thesis examines a range of processes known to influence DOC/colour production and release. A variety of field monitoring and laboratory measurements were undertaken to assess the upland blanket peat within the Oughtershaw Beck catchment in the Yorkshire Dales National Park, UK. The installation of drainage ditches was found to reduce both the carbon storage potential of the peat and the quality of upland catchment waters. Drainage lowered the depth of the water table across the peat by an average of 10 cm, enhanced the rate of microbial activity by 33 % and increased DOC and colour production in soil water solutions by 35 %, relative to an adjacent intact site that had not been drained. The greater level of aeration in the upper peat layers associated with a lowered water table also appeared to reduce the degree of surface saturation and the occurrence of overland flow (OLF), resulting in a greater volume of water being drawn down into the peat body. The reduced saturation levels caused the subsidence and compaction of the upper soil layers, which increased the bulk density and ultimately reduced the degree of macroporosity within the soil. In turn, this is thought to have increased the residence time and surface area over which percolating waters flow, which is likely to have enhanced the degree of interaction with decompositional products, and thus the mobility of DOC/colour. Drain blocking proved to be a highly effective technique for improving the carbon storage potential of blanket peat and ameliorating upland water quality. Blocking, using regularly spaced peat dams, successfully raised the height of the water table across the peat by an average of 4 cm, relative to the drained site. This increased the level of surface saturation and occurrence of OLF, whilst reducing rates of microbial activity and DOC production by 50 %. However, the volumetric changes associated with drainage appear to have resulted in permanent modifications to the structural and infiltration properties of the peat. Both the water table and the proportion of macropore flow at the drain-blocked site were reduced relative to the intact site, as were microbial activity rates, DOC concentration and colour levels. In addition, DOC composition was markedly different to that produced in the soil waters of both the intact and drained sites. The evidence suggests that a greater volume of percolating water travels through the peat matrix, relative to the intact site, which results in a pore water flushing mechanism and the preferential removal of labile un-coloured DOC components. Furthermore, the lower rate of microbial activity relative to the drained site provides evidence against the commonly quoted hypothesis that an enzyme-latch reaction may be sustained in a peat that has been re-wetted following water table drawdown. Although there was a strong association between DOC and colour, the relationshipvaried significantly between peat layers, land managements, and through time. This challenges the use of spectrophotometric analysis as an indirect method of DOC determination in peat soil waters as the use of a single regression equation resulted in the miscalculation of DOC concentrations by more than 50 %, as it failed to account of the fact that the fraction of coloured DOC components could vary significantly due to modifications made to microbial decomposition and mineralisation pathways and hydrological routing mechanisms.

Dissolved organic carbon (DOC) concentrations in UK rivers have been rising significantly, with the largest increases occurring in peat dominated catchments. These catchments are major sources of potable water in the UK and DOC compounds have adverse effects on many aspects of water quality, from serving as precursors for the formation of disinfection by-products and causing low residual chlorine (lin-ýiting its protection against biological contamination), to reducing aesthetic value. The potential effects of some major climate change predictions for northern regions on the quantity and quality of DOC produced in peatland catchments have therefore been examined. Such predictions include elevated atmospheric C02 concentrations (eC02). warmer temperatures (eTemp), an increased frequency of summer droughts and increased rainfall. Both eCO2 and eTemp increased leachate DOC concentrations with selective enrichment of recalcitrant phenolic compounds. Under eCO2, such increases were associated with the stimulation of plant inputs (biomass and exudation), reduced extracellular enzyme activities and suppressed DOC decomposition. Warmer conditions provided evidence for enzymic mobilization of DOC and phenolic compounds from the peat matrix. These treatments in combination (eCO2/eTemp) apparently interact to produce the highest concentrations of DOC and phenolic enrichment. Stable isotope (13C) labelling studies revealed that increased exudation of recently synthesized DOC potentially has a crucial role in this response. Successive droughts seemingly induced an increasing trend for DOC concentrations, due to an increased diversity of aerobic, aromatic degrading bacteria and enhanced enzyme activities stimulating mobilization of the peat matrix. Conversely, increased rainfall simulations showed reduced bacterial diversity and enzymic inhibition, conducive to the accumulation of high molecular weight DOC. Potential effects of climatic changes on biofilm communities in the recipient waters were also studied. Elevated C02 and eTemp in combination were found to increase DOC and phenolic compound production when photoautotrophs were present, but also to compromise the removal of these increased inputs by the biofilm heterotrophs. It is therefore proposed that increased DOC production (in the peatland system and by the biofilm) coupled with reduced biodegradation of this material could account for the rising DOC concentrations in UK rivers.

Inputs of DOC in precipitation were low and increased with the passage of rainfall through different canopies. Throughfall, stemflow, leachates from A horizons and litterfall were identified as sources of DOC, while B and C horizons in upland areas provide a sink. Throughfall and stemflow displayed high temporal variability in DOC concentrations, while soil leachates and peat waters exhibited strong seasonal patterns. DOC concentrations in throughfall, stemflow and A horizons were highest in the predominantly coniferous site. In the fall, DOC concentrations from A horizons in the deciduous site were significantly higher than those from the coniferous site.
Factors influencing DOC in peat waters are: (1) peat thermal regime, (2) water chemistry, and (3) water table position. Large storms ($>$30 mm precipitation) appear to be the primary factor influencing exports of DOC in streamflow, particularly following dry antecedant soil moisture conditions. Slow rates of water movement through compact deep peats ($>$60 cm depth) and adsorption of DOC in B and C horizons of this catchment obstruct exports of DOC, which over the 5.5 month study period, were minimal in comparison to inputs.

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.

Antihistamines are a group of pharmaceuticals that enter the environment and may affect microorganisms that regulate decomposing of organic matter and the release of carbon and nitrogen from soils. In this study I investigated if the antihistamine fexofenadine decreases the concentration of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) from humus. I used humus from two vegetation types (heath and meadow), and used a batch experiment approach, where humus was mixed with fexofenadine solutions (2000 ng/L and 20 000 ng/L). After ten days in room temperature, the samples with fexofenadine were compared with batches containing pure water solutions (control). I found differences in the concentration of DOC, DON and pH that were dependent on the studied vegetation types. There were higher concentrations of DOC and DON in heath (35.9 mg/L and 2.0 mg/L) than in the more nutrient rich meadow (9.2 mg/L and 0.5 mg/L). The latter vegetation type did also have a higher pH. In contrast to my hypothesis, the concentration of DOC and DON was not significantly affected by the fexofenadine. However, if considering a 90%-level of significance, there were a significant interaction effect where concentration of DOC decreased in meadow and increased it in heath. A possible vegetation specific effect of fexofenadin seems plausible as microbial biomass and activity in the vegetation types are known to differ. My findings cannot exclude that fexofenadine stimulates degradation of DOC in the more microbial active meadow humus, but not in the humus of heath where activities are lower.

Black carbon (BC) is an organic residue formed primarily from biomass burning (e.g., wildfires) and fossil fuel combustion. Until recently, it was understood that BC was highly recalcitrant and stabilized in soils over millennial scales. However, a fraction of the material can be solubilized and transported in fluvial systems as dissolved BC (DBC), which represents on average 10% of the global export of dissolved organic carbon (DOC) from rivers to coastal systems. The composition of DBC controls its reactivity, and it has been linked with a variety of in-stream processes that induce both carbon sequestration and evasion of CO₂ from aquatic systems, which suggest DBC may have a significant contribution within the global carbon cycle. The primary objectives for the thesis were to elucidate environmental factors that control the fate and transport of DBC in fluvial systems. Ultra-high resolution mass spectrometry was used to characterize DBC on a molecular scale whereas benzenepolycarboxylic acids were used to quantify and characterize BC in both dissolved and particulate phases (PBC). Sinks for polycondensed DBC were linked to a series of in-stream biogeochemical processes (e.g., photodegradation, metal interactions); whereas photooxidation of particulate charcoal led to production of DBC, suggesting photodissolution as a previously unrecognized source of DBC to fluvial systems. Coupling of DBC with PBC, however, was hydrologically constrained with sources varying over temporal scales and land use regimes. For DBC in particular, an enrichment of heteroatomic functionality was observed as a function of anthropogenic land use. Furthermore, land use coupled with stream order (a proxy for in-stream processing as defined by the River Continuum Concept) could explain significant spatial variability in organic matter (e.g., DOC) composition within an anthropogenically impacted system. With an increase in wildfire frequency projected with on-going climate change trends, parallel projections for increases in BC production are also expected. Furthermore, conversion of natural landscapes for urban and agricultural practices is also expected to continue in the coming decades. Thus, it is imperative to reach a comprehensive understanding of processes regulating the transport of DBC in fluvial systems with efforts to constrain future BC budgets and climate change models.

Thesis (Ph. D.)--University of California, San Diego, 2008.
Title from first page of PDF file (viewed March 18, 2008). Available via ProQuest Digital Dissertations. Vita. Includes bibliographical references.

The transport of dissolved organic carbon (DOC) and chromophoric dissolved organic matter (CDOM) from land to coastal environments strongly influences coastal ecosystems. The presence of first flush phenomena due to rainwater runoff traveling from land into waterways can greatly affect carbon fluxes to coastal areas. This research utilizes sensors, autosamplers, and standard watershed sampling in order to assess for the presence of first flush and its significance.

A rainfall simulator was built in order to collect runoff on two land use types. Time series data suggest that first flush of dissolved organic carbon was present for all rainfall intensities simulated on an impervious surface. At this location, approximately 40% to 51% of DOC flux occurred within the first 20% of runoff. At the permeable sampling location, first flush was observed in surface runoff collected during 12.7 and 25.4 mm hr^-1 simulated storms, with 31% and 26% of DOC flux occurring within the first 22% of runoff.

Seven storm events at two locations in the Neponset River Watershed, Massachusetts, USA were monitored to study the impact of storm events on DOC export from an urban watershed. Real-time CDOM fluorescence sensor measurements were better able to capture the variability present in riverine DOC and CDOM concentrations due to runoff influxes. Using modeled flow data, estimates of total DOC export fluxes during storms were compared to estimated total annual export. Based on these calculations, the seven sampled storm events account for 7 to 10 percent of the calculated yearly flux during 4 to 5 percent of the year. Additional work is needed to collect consistent year round data using sensors at these locations.

DOC was sampled throughout the Neponset River Watershed monthly for seven years. Increased concentrations were observed following storm events and snowmelt, and were an average of 28% greater than concentrations observed during dry periods. Based on daily sampling data in September 2011, monthly fluxes may be underestimated by 38% or overestimated by 35%. More frequent sampling allows for better certainty in estimations of monthly and yearly fluxes from the watershed, but must be balanced with logistical and cost constraints.

Kyoto University (京都大学)
0048
新制・課程博士
博士(農学)
甲第11622号
農博第1478号
新制||農||906(附属図書館)
学位論文||H17||N4015(農学部図書室)
23265
UT51-2005-D371
京都大学大学院農学研究科地域環境科学専攻
(主査)教授 谷 誠, 教授 小﨑 隆, 教授 太田 誠一
学位規則第4条第1項該当

Dissolved organic carbon (DOC) plays an important role in the global carbon (C) cycle because increases in aqueous C potentially contribute to rising atmospheric CO2 levels. Over the past few decades, headwater streams of the northern hemisphere have shown increased amounts of DOC coinciding with decreased acid deposition. Although the issue is widely discussed in the literature, a mechanistic link between precipitation composition and stream water DOC has not yet been proposed. In this study, the breakup of soil aggregates is hypothesized as the mechanistic link between reduced acid deposition and DOC increases in surface waters. Specific hypotheses state that soil aggregate dispersion (and the ensuing release of DOC from these aggregates) is driven by a decrease in soil solution ionic strength (IS, decreasing the tendency of flocculation) as well as a shift from divalent to monovalent cations (reducing the propensity for cation bridging) in soil solution. These hypotheses were tested on soil samples collected from several riparian zone and hillslope positions along three flagged transects in the acid-impacted Sleepers River Research Watershed in northeastern Vermont. To determine soil C content by landscape position, samples from transects spanning hilltop to hillslope and riparian area, as well as replicated hillslope and riparian samples (n=40) were analyzed. Aqueous soil extracts simulate the flushing of soils during hydrologic events (e.g. rain or snowmelt) and were used to test the effect of soil solution chemistry on DOC release. Extracts were prepared with solutions of varying IS (0-0.005M) and composition (CaCl2 and NaCl) on replicated soil samples (n=54) and changes in DOC release and aggregate size were monitored. As IS of the extraction solution increased, the amount of DOC in solution decreased, and aggregate size increased. This was presumably due to cations bridging and diffuse double layer effects. This effect was reversed in low ionic strength solutions where DOC release was significantly higher and average aggregate size was smaller. While extraction solution controlled the amount of C liberated, landscape position impacted the quality, but not quantity, of released DOC. This study is the first to propose a mechanistic link observed changes in DOC in surface waters and recovery from acidification and provides initial experimental evidence that soil aggregates indeed play a role in the generation of DOC.

Black carbon (BC), the incomplete combustion product from biomass and fossil fuel burning, is ubiquitously found in soils, sediments, ice, water and atmosphere. Because of its polyaromatic molecular characteristic, BC is believed to contribute significantly to the global carbon budget as a slow-cycling, refractory carbon pool. However, the mass balance between global BC generation and accumulation does not match, suggesting a removal mechanism of BC to the active carbon pool, most probable in a dissolved form. The presence of BC in waters as part of the dissolved organic matter (DOM) pool was recently confirmed via ultrahigh resolution mass spectrometry, and dissolved black carbon (DBC), a degradation product of charcoal, was found in marine and coastal environments. However, information on the loadings of DBC in freshwater environments and its global riverine flux from terrestrial systems to the oceans remained unclear. The main objectives of this study were to quantify DBC in diverse aquatic ecosystems and to determine its environmental dynamics. Surface water samples were collected from aquatic environments with a spatially significant global distribution, and DBC concentrations were determined by a chemical oxidation method coupled with HPLC detection. While it was clear that biomass burning was the main sources of BC, the translocation mechanism of BC to the dissolved phase was not well understood. Data from the regional studies and the developed global model revealed a strong positive correlation between DBC and dissolved organic carbon (DOC) dynamics, indicating a co-generation and co-translocation between soil OC and BC. In addition, a DOC-assistant DBC translocation mechanism was identified. Taking advantage of the DOC-DBC correlation model, a global riverine DBC flux to oceans on the order of 26.5 Mt C yr-1 (1 Mt = 1012 g) was determined, accounting for 10.6% of the global DOC flux. The results not only indicated that DOC was an important environmental intermediate for BC transfer and storage, but also provided an estimate of a major missing link in the global BC budget. The ever increasing DBC export caused by global warming will change the marine DOM quality and may have important consequences for carbon cycling in marine ecosystem.

Dissolved organic matter (DOM) is found in all freshwaters globally, by dissolving in rainwaterduring its path through soil and on to oceans via. rivers and streams. To provide potable water fit for human consumption, selected streams and rivers are used by either direct abstraction, or by diversion into reservoirs prior to treatment. For ca.100 years, chlorine and its compounds have been used by water treatment companies to disinfect water. However, research has shown that reactions between chlorine and DOM can produce compounds (disinfection by-products, or DBPs) which may be hazardous to human health. This thesis explores the relationship between catchment character, organic matter concentration, and the potential formation of DBPs. In particular, trihalomethanes (THMs) were measured as these are currently the only regulated DBPs in the UK. To achieve this, water samples were collected quarterly over one year from two contrasting catchments, to study seasonal variations in DOM concentration and character. A third catchment was also sampled, with similar catchment characters to the first two catchments, to determine whether geographical location and land use types affected the data. Each catchment was studied to see if catchment characteristics (e.g. class of vegetation, soil type or bedrock) could be mapped using a Geographical Information Systems (GIS) approach), to observe any effects on DOM and/or the DBPs found in treated water, with the aim of producing a risk assessment map to aid the choice of future abstraction locations for drinking water. Hence, samples were chlorinated and chloraminatedin the laboratory before being analysed for DBP formation and residual chlorine concentrations were measured. Catchment specific GIS derived data were statistically analysed with water chemistry data, and detected relationships were explored statistically. Major findings include medium to strong positive correlations between the standardised THM4 (STHM4 - the concentration of THM4 formed from 1 mg L-1 dissolved organic carbon (DOC)) concentration and geology, where an increase of the area of inland rock in a catchment increases STHM4 concentration. Medium strength positive correlations were found between STHM4 and vegetation classes, where, as the area of acid grassland, and heather increase, so does the concentration of STHM4. Negative relationships were discovered showing the obverse, where, as loamy and clayey floodplain soils with naturally high groundwater increased in area, STHM4 concentration dropped (at the Hampshire Avon ii and Conwy catchments combined). The occurrence of coniferous woodland in a catchment was found to correlate with the CHCl3 formation potential of waters (Pearsons, f=0.530, p= < 0.05, n=20), supporting findings in published literature. Laboratory based chlorination and chloramination of sample waters, followed by gas chromatography provided DBP data, specifically THM4. These data show that more chloroform was formed after chlorination than chloramination, and that chloramination formed 3 times more CHBr3 (another THM4 compound) than chlorination, under laboratory formation potential conditions. Results showed that the chlorination of water prior to DOM removal could result in a THM4 concentrations 5 times greater than the current UK regulatory limit, per mg L-1 dissolved organic carbon (DOC), whereas chloramination forms ca.5 times less than the current UK regulation per 1 mg L-1 DOC. However, chlorination of water prior to DOM removal is never done in practice, so this data provides information on the composition of the organic matter and whether DOM from a specific catchment contains specific components that are responsible for an increase in a specific DBP. Data also show that increasing organic nitrogen or organic carbon does not necessarily increase nitrogenous or carbonaceousDBPs (N-DBPs or C-DBPs). However, importantly, data shows that an increase in the area of land use classed as 'urban', results in an increase in DON (likely due to human influences) in the water draining from them, posing potential issues for eutrophication in downstream water bodies and the formation of N-DBPs at water treatment works. Whilst N-DBP detection was explored from several different angles, the development of a definitive method was not possible due to very low N-DBP concentrations, time and financial constraints. However, various methods were adapted to aid in the detection of them, showing promising initial results, providing the background for future projects into the discovery of a suite of N-DBPs such as haloacetonitriles and halonitromethanes. Finally, the data in this thesis have been inputted into maps for each major catchment to present data with a high visual impact, but also to illustrate land use types that have been found to correlate with increases in DBPs and specific nutrients in the water draining from them. However, the high variation in DOM concentration and character from site to site make extrapolation of these risk assessment data, to other catchments, unsafe. Nevertheless, collection of data from a catchment (similar to the work presented here) where a new water abstraction location is desired can prove advantageous in providing information to utility companies of what difficulties they may encounter when treating the water. Though this can be done by grab sampling at each site of interest, this can prove costly and timely and involves both field and laboratory based work aspects, wheras the method presented here requires less cost and time, once the method is initialised, to derive data of similar value. Despite the fact that disinfection performance would always trump DBP minimalisation, this is likely to be a vital tool in ensuring the provision of safe and healthy water fit for the consumption of an ever increasing human population.