The objective of this thesis is to improve the understanding of what processes and mechanism affects the distribution of polychlorinated biphenyls (PCBs) and organic carbon in coastal sediments. Because of the strong association of hydrophobic organic contaminants (HOCs) such as PCBs with organic matter in the aquatic environment, these two entities are naturally linked. The coastal environment is the most complex and dynamic part of the ocean when it comes to both cycling of organic matter and HOCs. This environment is characterised by the largest fluxes and most diverse sources of both entities. A wide array of methods was used to study these processes throughout this thesis. In the field sites in the Stockholm archipelago of the Baltic proper, bottom sediments and settling particulate matter were retrieved using sediment coring devices and sediment traps from morphometrically and seismically well-characterized locations. In the laboratory, the samples have been analysed for PCBs, stable carbon isotope ratios, carbon-nitrogen atom ratios as well as standard sediment properties. From the fieldwork in the Stockholm Archipelago and the following laboratory work it was concluded that the inner Stockholm archipelago has a low (≈ 4%) trapping efficiency for freshwater-derived organic carbon. The corollary is a large potential for long-range waterborne transport of OC and OC-associated nutrients and hydrophobic organic pollutants from urban Stockholm to more pristine offshore Baltic Sea ecosystems. Theoretical work has been carried out using Geographical Information Systems (GIS) and statistical methods on a database of 4214 individual sediment samples, each with reported individual PCB congener concentrations. From this work it was concluded that the continental shelf sediments are key global inventories and ultimate sinks of PCBs. Depending on congener, 10-80% of the cumulative historical emissions to the environment are accounted for in continental shelf sediments. Further it was concluded that the many infamous and highly contaminated surface sediments of urban harbours and estuaries of contaminated rivers cannot be of importance as a secondary source to sustain the concentrations observed in remote sediments. Of the global shelf PCB inventory < 1% are in sediments near population centres while ≥ 90% is in remote areas (> 10 km from any dwellings). The remote sub-basin of the North Atlantic Ocean contains approximately half of the global shelf sediment inventory for most of the PCBs studied.

The global carbon cycle is intimately linked with the earth’s climate system. Knowledge about carbon cycling in the biosphere is therefore crucial for predictions of climate change. This thesis investigates the carbon dioxide balance of Swedish boreal lakes, its regulation, significance to the carbon budget of the boreal landscape, and sensitivity to climate change. Swedish boreal lakes were almost exclusively supersaturated in CO2 with respect to the atmosphere, resulting in an emission of CO2 from lakes to the atmosphere. Lake pCO2 was closely related to the concentration of terrigenous dissolved organic carbon (DOC), indicating that the utilization of terrigenous DOC by lake bacteria is a major source of CO2. This conclusion is supported by independent field studies, showing that net plankton respiration accounts for most of the CO2 emitted from Swedish boreal lakes, while photochemical mineralization and sediment respiration were less important. Mineralization of terrigenous DOC and subsequent emission of CO2 from lakes to the atmosphere was a major carbon loss factor in 21 major Swedish boreal catchments, removing 30-80% of the organic carbon exported from terrestrial soils to surface waters. Lake CO2 emission is in the same order of magnitude as organic carbon accumulation in boreal forest soils, and should therefore be included in the carbon budget of the boreal landscape. In a set of nearly 5000 global lakes, DOC concentration was a much more important regulator of lake pCO2 than temperature. Climate change will therefore affect the carbon balance of lakes primarily via alterations in terrestrial DOC export, rather than via changes in temperature per se. Both current observations and models of future climate suggest an increasing export of terrigenous DOC from many Scandinavian catchments. Hence, there probably is a current trend towards higher CO2 emission from Swedish boreal lakes, which is likely to continue in the future.

Two small bordering catchments in Bispgården, Central Sweden, wereinvestigated in regard to soil solution and stream water chemistry during the frostfree seasons of 2003-2007. Both catchments were drained by first order streams,Fanbergsbäcken and Gråbergsbäcken, and in Fanbergsbäckens catchment anextensive investigation of the soil and soil solution chemistry was conducted bylysimeter and centrifugation sampling. The area of intensive soil solutioninvestigation was situated in a slope towards a stream incorporating a rechargearea, with podzolic soil, and a discharge area close to the stream with an arenosolsoil. Samples were continuously taken in both the recharge- and the discharge areaof the slope, and stream water was sampled in the streams of both catchments. Themain variables of interest of the study were the interactions, the influence ofdissolved organic carbon and the effects of wood ash application to soil solutionand stream water.The natural variations and the interactions between soil solution and streamwater were monitored during 2003-2004. In soil solution, most of the investigatedsubstances tended to increase during the growing season, due to weathering andmicrobial degradation of biota. Ca, Mg, Al and Fe were highly associated todissolved organic carbon (DOC) throughout the catchment. The low molecularfraction of DOC seemed to have a higher impact on the soil processes in therecharge area, while high molecular DOC was more important for transport ofcations in the discharge area and the stream water.The concentration of different substances in the two streams differedsignificantly, even though the catchments were similar in size, shape andforestation. The seasonal patterns of most of the substances measured weresignificantly correlated between the streams, however. Cations and pH correlatedwell with DOC and flow. The flow pattern driven by precipitation seems to be thedriver of the stream water chemistry.Wood ash was applied at a dosage of 3 ton/ha to one of the catchments in theautumn of 2004, to investigate the initial effects on the soil solution- and streamwater chemistry. WAA is recommended by the Swedish Forest Agency tocounteract acidification in soil and runoff that may be caused by an intensivebiomass harvesting. The impact of the WAA was studied during 2005-2006.Compared to the control temporarily higher concentrations of K, Ca and SO4 wereobserved in the soil solution of the ashed area. In the stream water the effects of theWAA were easier to distinguish due to higher sampling frequency. The strongesteffect was seen for K, but increases in the stream water were also noted for DOC,Ca, Mg, Si, Cl and malonate. No increase in pH could be statistically verifiedhowever, and overall the initial effects of the WAA seem mild. / Två angränsande avrinningsområden i Bispgården i centrala Sverigeundersöktes under den snöfria säsongen 2003-2006. Båda avrinningsområdenadränerades av första ordningens bäckar och i det ena, Fanbergsbäckensavrinningsområde, gjordes en omfattande undersökning av mark och markvattenkemin.Markvatten provtogs genom centrifugering och med lysimetrar.Provtagningen gjordes i inströmningsområdet där jordmånen var en typiskpodzol samt närmare bäcken, i utströmningsområdet, där jordmånen var enarenosol. Bäckvatten provtogs i båda avrinningsområdena. Interaktioner mellanmark, markvatten och bäckvatten undersöktes med särskilt fokus på inverkan avorganiskt kol samt påverkan av askåterföring.De naturliga variationerna i markkemin samt interaktionerna mellan mark- ochbäck vatten undersöktes 2003-2004. I markvatten ökade merparten av de studeradeämnena under provtagningssäsongen beroende av ökad vittring och recirkulationav biota och fallförna. Ca, Al och Fe var i stor utsträckning associerade till löstorganiskt kol (DOC). Den lågmolekylära fraktionen av DOC hade en störreinverkan på markprocesserna i inströmningsområdet, medan den högmolekyläradelen var viktigare för transport av katjoner i utströmningsområdet samt ibäckvattnet.Koncentrationsnivåerna av olika substanser i bäckarna uppvisade skillnadertrots avrinningsområdenas yttre likheter med avseende på storlek, form ochbeskogning. Trots de kvantitativa skillnaderna erhölls emellertid liknandesäsongsvariationer i koncentrationerna, vilket indikerade att kemin i huvudsakstyrdes av mängden DOC som i sin tur berodde av avrinningen som drevs avnederbörden. Höga halter av Ca, Mg, Al och Fe återfanns associerade tillhögmolekylärt DOC i bäckvattnet i en utsträckning som inte rapporterats tidigare.På hösten 2004 spreds 3 ton aska/ha till Fanbergsbäckens avrinningsområde föratt undersöka de initiala effekterna på mark- och bäckvatten kemin. Askåterföringbör ske minst en gång per omloppstid vid helträdsavverkning, i enlighet medSkogsstyrelsens rekommendationer, främst för att motverka försurning i mark ochavrinnande vatten som antas uppstå vid intensivt uttag av biomassa. De initialaeffekterna av askåterföringen på mark- och bäckvattnets kemi studerades under2005-2006 och Gråbergsbäcken kunde användas som obehandlad kontroll vidundersökning av vattenkemin i Fanbergsbäcken. I undersökningen av markvattenviåterfanns stora säsongsvariationer, vilket gjorde det svårt att urskilja eventuellaeffekter av askåterföringen. Tillfälligt högre värden av K, Ca och SO4 återfannsdock i det askade området i jämförelse med kontrollområdet. På grund av högreprovtagningsfrekvens i bäckvattnet var det lättare att påvisa förändringar ibäckvatten kemin. Framförallt märktes en signifikant ökning av K jämfört medkontrollbäcken. Sådana ökningar, om än inte lika markanta återfanns också förDOC, Ca, Mg, Si, Cl och malonat. En tendens till ökat pH kunde observeras, mendenna kunde inte verifieras statistiskt. De initiala effekterna av askåterföringen varsåledes till synes milda, och den eftertraktade pH-effekten erhölls ej i dennaundersökning.

Atmospheric aerosols may be emitted directly as particles (primary) or formed from gaseous precursors (secondary) from different natural and anthropogenic sources. The highly populated South and East Asia regions are currently in a phase of rapid economic growth to which high emissions of carbonaceous aerosols are coupled. This leads to generally poor air quality and a substantial impact of anthropogenic aerosols on the regional climate. However, the emissions of different carbon aerosol components are still poorly constrained. Water-soluble organic carbon (WSOC) is a large (20-80%) component of carbonaceous aerosols that can absorb solar light and enhance cloud formation, influencing both the direct and indirect climate effects of the aerosols. A novel method for carbon isotope-based studies, including source apportionment, of the WSOC component of ambient aerosols was developed and tested for recovery efficiency and the risk of contamination using both synthetic test substances and ambient aerosols (paper I). The application of this method for the source apportionment of aerosols in South and East Asia shows that fossil fuel input to WSOC is significant in both South Asia (about 17-23%) highly impacted by biomass combustion practices and in East Asia (up to 50%) dominated by fossil energy sources (papers II, III, IV). Fossil fraction in WSOC in the outflow from northern China is considerably larger than what has been measured in South Asia, Europe and USA (paper IV). A trend of enrichment in heavy stable carbon isotopes in WSOC with distance the particles have been transported from the source is observed in the South Asian region (papers II, III). Dual-isotope (Δ14C and δ13C) analysis demonstrates that WSOC is highly influenced by atmospheric aging processes. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Submitted.</p>

Inland waters have long been neglected in the global carbon cycle. They represent only 2,8% of the land area, but it has come clear that inland waters play a key role in the transformation of terrestrial fixed carbon to the atmosphere. Human activities do have an impact on the carbon cycling and it is important to understand how these changes affects natural biogeochemical and climatological processes. The purpose of this report was to investigate how forestry impacts the emission of carbon dioxide from boreal lakes and to evaluate which role lakes play in the global carbon cycle. The study was accomplished as a literature study and the search words that have been used are carbon cycling, carbon dioxide, forestry, boreal lakes, dissolved organic carbon and pCO2. The results show that in many studies does forestry increase the export of dissolved organic carbon from terrestrial environments to boreal lakes. This increase subsidies the net heterotrophy in boreal lakes, making them net sources of carbon dioxide to the atmosphere. The processes behind increased concentrations and emissions are however complex and factors like local topography, hydrology and climate are thought to have impacts on how much carbon dioxide that is produced at a given level of dissolved organic carbon. Forestry seems to have an increasing effect on the carbon dioxide emissions, but the key drivers behind this process are expressed differently between regions and the reasons underlying these differences remain to be explored in order to make precise global carbon models.

Soil organic N (SON) comprises 90% of all N in surface soils, yet as much as half remains in forms which are chemically unknown or, at best, poorly understood. Analytical methods such has pyrolysis field-ionization mass spectrometry (Py-FIMS) and 15N cross polarization magic-angle spinning nuclear magnetic resonance (CPMAS-NMR) spectroscopy are widely used for the characterization of SON; however, these methods have limitations which contribute to the gaps in our understanding of SON chemistry. For example, Py-FIMS may produce heat-induced secondary compounds, and 15N-NMR may lack sensitivity and resolution for experiments at natural 15N abundance. X-ray absorption near edge structure (XANES) spectroscopy probes the bonding environment of individual elements. The application of this technique to complex environmental samples such as soil is still in its infancy, but early studies suggest that this technique may help resolve SON molecular structure. This dissertation sought to develop and apply synchrotron-based N and C K-edge XANES spectroscopy to the study of soil and soil extracts to determine the structures in which SON is bound. In these studies, Py-FIMS was coupled with XANES as a corroboratory technique.<p> Initial methodological development resulted in a calibration method whereby N2 gas generated in ammonium-containing salts was used to calibrate a soft X-ray beamline at the N K-edge. Although XANES can produce secondary compound artifacts, contrary to early assertions that it is a non-destructive technique, it was shown in a second study that beam-induced decomposition can be minimized by moving the beam to a fresh spot between scans.<p> Three applied studies exploring SON composition were conducted. These studies followed a spatial gradient ranging from the landscape scale, through a rhizosphere study, and ended with a study of glomalin-related soil protein (GRSP). Glomalin-related soil protein is a persistent soil glycoprotein of arbuscular mycorrhizal origin (AMF) implicated in aggregation and long-term C and N storage. Nitrogen and C K-edge XANES and Py-FIMS were used in all studies, and GRSP was further characterized using proteomics techniques.<p> Soil organic N composition was largely controlled by topographic position, and to a lesser degree, by cultivation. Divergent (i.e., water shedding) positions were enriched in carbohydrates and low molecular weight lignins, whereas convergent, depressional and level positions showed enrichment in lipid-type compounds. These differences were attributed to tillage-induced redistribution of soil, and water movement from upper to lower slope positions. Nitrogen XANES revealed a unique form of organic N, identified as N-bonded aromatics, particularly in the divergent positions.<p> Rhizosphere soil was enriched in higher molecular weight lipid-type materials and depleted in low molecular weight polar compounds. This was attributed to increased input of fresh plant material and higher microbial turnover in the rhizosphere. Nitrogen-bonded aromatics also were detected in the rhizosphere.<p> The GRSP extracts were characterized as mostly proteinaceous, but also contained many co-extracted, non-protein compounds. Despite being previously described as a glycoprotein, only weak carbohydrate signals were observed. Proteomics-based assessment of GRSP showed no homology to any proteins of AMF origin, instead showing homology with thioredoxin and with heat-stable soil proteins. This may be because protein databases do not yet contain glomalin-related sequences, or that glomalin is homologous to non-AMF soil proteins.<p> This dissertation demonstrated that N XANES is a sensitive and novel method for characterizing SON, and can be used complementarily with other analytical techniques such as Py-FIMS and proteomics. The continued development of XANES will provide a useful tool for SOM research into the future.

I analyzed the 21 year dynamics of dissolved organic carbon (DOC) in 55 lakes in five sites across Eastern Canada in relation to regional and global variables. Regional variables included total solar radiation (TSR), precipitation (PPTN), air temperature (T) and sulfate deposition (SO4). Global variables included the Southern Oscillation Index (SOI), North Atlantic Oscillation (NAO) and Pacific Decadal Oscillation (PDO). A synchronous pattern in DOC was found among lakes within each region; however, a synchronous pattern in DOC was not found between sites, except for Kejimkujik and Yarmouth which were only 80 km apart from each other. This suggested that the variation of the long-term DOC pattern was in response to the temporal pattern of regional variables, and it supports the recent understanding that regional factors have a strong influence on many lake properties. Significant long-term trends in DOC were not evident except at the Experimental Lakes Area (ELA), where an increase in DOC was observed together with a decrease in summer TSR and an increase in summer precipitation. Annual mean air temperature has increased at the Nova Scotia and Turkey lakes sites over the study period. The relationship between the long-term pattern in DOC with the regional and global variables was analyzed for each study site to determine the key variables that could best explain the variation in the long-term pattern in DOC. TSR and PPTN were important independent variables across all sites, except for the Turkey Lakes Watershed site (TLW). Summer TSR (annual TSR for Kejimkujik and Yarmouth) had a negative relationship, while summer precipitation had a positive relationship with the long-term DOC pattern for all sites except TLW. TSR and PPTN explained 78%, 49% and 84% of the variation in the long-term DOC pattern at Dorset, ELA, and Nova Scotia (NS) sites, respectively. In contrast, the long-term pattern in DOC at TLW only had a weak relationship with the regional and global variables considered. A General model was developed to compare the strength of the response of DOC to the regional variables among sites. Therefore, only the variables which had a significant linear correlation with DOC across sites were selected. If a site had no variables in common with other sites, it was excluded from the general model. This resulted in TLW being excluded from the general model because the long-term DOC pattern at TLW was not significantly correlated with any regional variables. The best general model included TSR from Dorset, ELA and NS sites and precipitation from only the NS site. The strengths of the response of DOC to precipitation were weak at Dorset and ELA compared to NS, therefore, they were excluded. The general model explained 91% of the site-to-site variation of DOC among sites. Among them, TSR was an important negative variable which contributed 56% of the explanation to the general model. Precipitation at NS was an important positive variable for the general model. It contributed 34% of the explanation to the model. As the response of the long-term DOC pattern to the changes of environmental variables (TSR and PPTN) was very strong at NS, the NS site dominated the general model, and its temporal (year-to-year) variation in the long-term DOC pattern explained 60% of the site-to-site variation of DOC in Eastern Canada. The other two sites, Dorset and ELA, had weak contributions (20% and 11%, respectively) to the general model.

Understanding the mechanisms of non-point source carbon and nutrients in urban watersheds will help to develop policies to maintain surface water quality and prevention of eutrophication. The purpose of this dissertation is to investigate the impact of sodium on carbon and nutrient leaching from the two main contributors; soil and leaf litter, and calculate the sodium exports in a humid subtropical urban river basin. The first chapter reviews the current literature on urbanization in watersheds. Chapter II quantifies the carbon and nutrient in intact soil core leachates and in water extractable solution from urban soils collected from 33 towns and cities across the state of Texas. Chapter III investigates the impact of sodicity and salinity on water extractable organic carbon and nitrogen from vegetation. Chapter IV investigates the export of sodium and chloride from the upper Trinity River basin. The results derived from this study indicate that sodium exports are elevated in urban watersheds and further that sodium in irrigation water elevates the loss of carbon and nutrients from both watershed soil and senesced vegetation and that this may contribute to high concentrations in urban freshwaters.

Allochthonous carbon can be a large proportion of the carbon budget in northern temperate and boreal lakes. This thesis uses stable carbon and oxygen isotopes to examine the fate of allochthonous dissolved organic matter (DOM) in northern temperate lakes, and to determine the importance of dissolved organic carbon (DOC) in lake carbon mass balances and in the δ¹³C of lake sediments. To use stable isotopes as a tool for studying DOC loss and sedimentation within lakes requires an understanding of processes that affect the δ¹³C and δ¹⁸O in aquatic systems. Photolysis is one mechanism that can account for the large allochthonous DOC loss within northern temperate lakes. There is, however, little research examining the effects of photolysis on stable isotopes (e.g. δ¹³C and δ¹⁸O) in aquatic systems, or how photodegradation of DOM affects the δ¹³C of lake sediments. To study the effects of DOM photodegradation on carbon and oxygen isotopes, stream waters from catchments with varying peatland coverage were incubated in Tedlar bags placed in water baths under natural sunlight. Results from three streams flowing into two oligotrophic headwater lakes (Harp and Dickie Lakes) indicate that O₂ consumption rates and dissolved inorganic carbon (DIC) production rates were an order of magnitude greater in light exposed treatments than in dark treatments, suggesting that light mediated processes control O₂ consumption and DIC production in incubations. The similarity between filtered, inoculated, and sterile treatments, indicate that photolysis was the dominant O₂ consuming and DIC producing process in the incubations, while the contribution of respiration to these processes was not detectable. Differences in both O₂ consumption rates and DIC production rates (normalized to DOC loss) among streams suggest that DOM photolability was an important factor in both O₂ loss and DIC production on a volumetric basis. A concomitant increase in δ¹⁸O-O₂ was observed with O₂ loss indicating that during the photo-oxidation of DOM, the lighter ¹⁶O isotopomer was preferentially consumed in the oxidation of DOC to CO₂. Fractionation factors for respiration, photolysis and other abiotic reactions were not a function of O₂ consumption rates and ranged between 0.988 and 0.995, which lies outside the range published for respiration (0.975-0.982). These are the first published photolytic fractionation factors. The δ¹³C-DIC produced collectively by photolysis, respiration, and other abiotic reactions in incubations exposed to natural sunlight ranged between –23‰ and –31‰, and were similar in the light incubations for each treatment, but different among streams. Together, the light and dark incubation data suggest that photolysis and other abiotic reactions were largely responsible for the DIC concentration and δ¹³C-DIC changes observed, while respiration is a relatively minor contributor. During the incubations, as DOC photodegraded to CO₂, the lighter ¹²C isotope was preferentially mineralized (or the moieties cleaved were depleted in ¹³C) leaving the residual δ¹³C-DOC 1‰ to 4‰ enriched, creating enrichment (ε) values up to ~–3‰. The change in final δ¹³C-DOC after DOM photodegradation was different for each inflow, ranging from ~1 ‰ to 8.0 ‰, and provides an average enrichment of –2.1‰ (Harp Inflows ε: –1.2‰; Dickie Inflows ε: –3.4‰). These ε values are in agreement with the average ε from previous incubations on 3 of the inflows and 3 published studies based on UV exposed bog water (Osburn et al., 2001), riverine waters (Opsahl and Zepp, 2001), and lyophilized Juncus leachate dissolved in lake water (Vähätalo and Wetzel, 2008) (average ε = –2.9‰). The structure of DOM changed during photolysis. Absorbance data indicated that the aromaticity, colour, UV absorption and the average molecular size of the DOC decreased. Additionally, after exposure to sunlight, C/N ratios of the DOC changed from high values (24-55), indicative of terrestrial inputs, to lower values (4-13) traditionally thought to be representative of algal or microbial inputs. This contradicts the conventional view that terrestrial DOC has C/N ratios >20, and shows that abiotic processes can alter allochthonous carbon structure and the residual allochthonous carbon can have C/N values similar to, or overlapping with, C/N ratios expected from algal or microbial carbon. With the loss of 61-90% of the DOC, the particulate organic carbon (POC) created accounted for 20-90% of the DOC lost. Values of δ¹³C-POC ranged from –25.7‰ to –27.7‰, with 80% of the samples within 1‰ of the initial δ¹³C-DOC indicating that the particulate carbon created from the photodegradation of DOM that settles to the lake sediments could be isotopically similar to the source DOC. Overall, these incubations indicate that the photodegradation of DOM can affect both concentrations and isotopes of O₂, DIC, DOC, and POC of the stream waters flowing into Harp and Dickie Lakes and are important to consider in lake dynamics of high DOC retention lakes. Two independent methods were used to examine the importance of allochthonous DOC to lake sediments. The first method used a two end-member mixing model to estimate the proportion of allochthonous and autochthonous carbon within the lake sediments. Inflow δ¹³C-POC data, δ¹³C-leaf litter measurements, and DOC photodegradation experiments were used to calculate average annual δ¹³C-POC values for the allochthonous end member. The average annual δ¹³C-POC values for the autochthonous end member were calculated using estimates of productivity, surface δ¹³C-CO₂ values and estimated average annual fractionation factors. Average annual δ¹³C-POC values from allochthonous and autochthonous sources for these lakes were distinct. Using the end members to calculate the relative contributions of allochthonous and autochthonous carbon to lake sediments revealed that the δ¹³C of the lake sediment can be significantly affected by the ratio of autochthonous and allochthonous contributions. Furthermore, peaks in the allochthonous contributions of carbon accompany the δ¹³C peaks in the sediment records to the lake sediments. This suggests that climate change and/or anthropogenic changes to the landscape, and the concomitant changes in DOC inputs to lakes, can be recorded in the sediment record indicating that sediment records are not just productivity signals, but also mass balance signals in high DOC retention lakes. In the second method carbon isotope budgets were completed to accompany the carbon mass budgets for Harp and Dickie Lakes. Mass-weighted average annual δ¹³C-DOC values from the inflows and outflows and δ¹³C-DIC values from the inflows varied by 0.2‰ to 1.3‰, suggesting the values are well constrained. Conversely, the range of weighted δ¹³C-DIC values from the outflows were larger (2.2‰) than those of the inflows. Calculated δ¹³C values of the lake sediment were not equal to the measured δ13C values of the lake sediments for either Harp or Dickie Lakes suggesting a problem lies within the mass balances, or the weighted average annual δ¹³C values used in the isotope budgets. To examine the sensitivity of the average annual weighted δ¹³C values for the carbon entering and exiting the lakes, and the mass of carbon entering the lakes δ¹³C of the lake sediments, a mass and isotope budget model was created. The model indicated that the δ¹³C of the lake sediments is sensitive to a number of parameters including the amount of DOC entering the lake, the δ13C-CO2 evaded from the lake, the areal water discharge rate (qs), the gas exchange coefficient (k), and pH. Many of these parameters required adjustments for the masses of carbon to match those presented in the mass balances suggesting that the mass balances averaged over 8 years have errors associated with them. However, changing the DOC load to the lakes in the model by the variability observed over all the years of the mass balances) indicates that the isotopic signature of the lake sediment could change by up to 2.5‰. This isotope change is large enough to account for the historical δ¹³C changes observed in the δ¹³C sediment record, suggesting that allochthonous DOC can drive the sediment record.

Allochthonous carbon can be a large proportion of the carbon budget in northern temperate and boreal lakes. This thesis uses stable carbon and oxygen isotopes to examine the fate of allochthonous dissolved organic matter (DOM) in northern temperate lakes, and to determine the importance of dissolved organic carbon (DOC) in lake carbon mass balances and in the δ¹³C of lake sediments. To use stable isotopes as a tool for studying DOC loss and sedimentation within lakes requires an understanding of processes that affect the δ¹³C and δ¹⁸O in aquatic systems. Photolysis is one mechanism that can account for the large allochthonous DOC loss within northern temperate lakes. There is, however, little research examining the effects of photolysis on stable isotopes (e.g. δ¹³C and δ¹⁸O) in aquatic systems, or how photodegradation of DOM affects the δ¹³C of lake sediments. To study the effects of DOM photodegradation on carbon and oxygen isotopes, stream waters from catchments with varying peatland coverage were incubated in Tedlar bags placed in water baths under natural sunlight. Results from three streams flowing into two oligotrophic headwater lakes (Harp and Dickie Lakes) indicate that O₂ consumption rates and dissolved inorganic carbon (DIC) production rates were an order of magnitude greater in light exposed treatments than in dark treatments, suggesting that light mediated processes control O₂ consumption and DIC production in incubations. The similarity between filtered, inoculated, and sterile treatments, indicate that photolysis was the dominant O₂ consuming and DIC producing process in the incubations, while the contribution of respiration to these processes was not detectable. Differences in both O₂ consumption rates and DIC production rates (normalized to DOC loss) among streams suggest that DOM photolability was an important factor in both O₂ loss and DIC production on a volumetric basis. A concomitant increase in δ¹⁸O-O₂ was observed with O₂ loss indicating that during the photo-oxidation of DOM, the lighter ¹⁶O isotopomer was preferentially consumed in the oxidation of DOC to CO₂. Fractionation factors for respiration, photolysis and other abiotic reactions were not a function of O₂ consumption rates and ranged between 0.988 and 0.995, which lies outside the range published for respiration (0.975-0.982). These are the first published photolytic fractionation factors. The δ¹³C-DIC produced collectively by photolysis, respiration, and other abiotic reactions in incubations exposed to natural sunlight ranged between –23‰ and –31‰, and were similar in the light incubations for each treatment, but different among streams. Together, the light and dark incubation data suggest that photolysis and other abiotic reactions were largely responsible for the DIC concentration and δ¹³C-DIC changes observed, while respiration is a relatively minor contributor. During the incubations, as DOC photodegraded to CO₂, the lighter ¹²C isotope was preferentially mineralized (or the moieties cleaved were depleted in ¹³C) leaving the residual δ¹³C-DOC 1‰ to 4‰ enriched, creating enrichment (ε) values up to ~–3‰. The change in final δ¹³C-DOC after DOM photodegradation was different for each inflow, ranging from ~1 ‰ to 8.0 ‰, and provides an average enrichment of –2.1‰ (Harp Inflows ε: –1.2‰; Dickie Inflows ε: –3.4‰). These ε values are in agreement with the average ε from previous incubations on 3 of the inflows and 3 published studies based on UV exposed bog water (Osburn et al., 2001), riverine waters (Opsahl and Zepp, 2001), and lyophilized Juncus leachate dissolved in lake water (Vähätalo and Wetzel, 2008) (average ε = –2.9‰). The structure of DOM changed during photolysis. Absorbance data indicated that the aromaticity, colour, UV absorption and the average molecular size of the DOC decreased. Additionally, after exposure to sunlight, C/N ratios of the DOC changed from high values (24-55), indicative of terrestrial inputs, to lower values (4-13) traditionally thought to be representative of algal or microbial inputs. This contradicts the conventional view that terrestrial DOC has C/N ratios >20, and shows that abiotic processes can alter allochthonous carbon structure and the residual allochthonous carbon can have C/N values similar to, or overlapping with, C/N ratios expected from algal or microbial carbon. With the loss of 61-90% of the DOC, the particulate organic carbon (POC) created accounted for 20-90% of the DOC lost. Values of δ¹³C-POC ranged from –25.7‰ to –27.7‰, with 80% of the samples within 1‰ of the initial δ¹³C-DOC indicating that the particulate carbon created from the photodegradation of DOM that settles to the lake sediments could be isotopically similar to the source DOC. Overall, these incubations indicate that the photodegradation of DOM can affect both concentrations and isotopes of O₂, DIC, DOC, and POC of the stream waters flowing into Harp and Dickie Lakes and are important to consider in lake dynamics of high DOC retention lakes. Two independent methods were used to examine the importance of allochthonous DOC to lake sediments. The first method used a two end-member mixing model to estimate the proportion of allochthonous and autochthonous carbon within the lake sediments. Inflow δ¹³C-POC data, δ¹³C-leaf litter measurements, and DOC photodegradation experiments were used to calculate average annual δ¹³C-POC values for the allochthonous end member. The average annual δ¹³C-POC values for the autochthonous end member were calculated using estimates of productivity, surface δ¹³C-CO₂ values and estimated average annual fractionation factors. Average annual δ¹³C-POC values from allochthonous and autochthonous sources for these lakes were distinct. Using the end members to calculate the relative contributions of allochthonous and autochthonous carbon to lake sediments revealed that the δ¹³C of the lake sediment can be significantly affected by the ratio of autochthonous and allochthonous contributions. Furthermore, peaks in the allochthonous contributions of carbon accompany the δ¹³C peaks in the sediment records to the lake sediments. This suggests that climate change and/or anthropogenic changes to the landscape, and the concomitant changes in DOC inputs to lakes, can be recorded in the sediment record indicating that sediment records are not just productivity signals, but also mass balance signals in high DOC retention lakes. In the second method carbon isotope budgets were completed to accompany the carbon mass budgets for Harp and Dickie Lakes. Mass-weighted average annual δ¹³C-DOC values from the inflows and outflows and δ¹³C-DIC values from the inflows varied by 0.2‰ to 1.3‰, suggesting the values are well constrained. Conversely, the range of weighted δ¹³C-DIC values from the outflows were larger (2.2‰) than those of the inflows. Calculated δ¹³C values of the lake sediment were not equal to the measured δ13C values of the lake sediments for either Harp or Dickie Lakes suggesting a problem lies within the mass balances, or the weighted average annual δ¹³C values used in the isotope budgets. To examine the sensitivity of the average annual weighted δ¹³C values for the carbon entering and exiting the lakes, and the mass of carbon entering the lakes δ¹³C of the lake sediments, a mass and isotope budget model was created. The model indicated that the δ¹³C of the lake sediments is sensitive to a number of parameters including the amount of DOC entering the lake, the δ13C-CO2 evaded from the lake, the areal water discharge rate (qs), the gas exchange coefficient (k), and pH. Many of these parameters required adjustments for the masses of carbon to match those presented in the mass balances suggesting that the mass balances averaged over 8 years have errors associated with them. However, changing the DOC load to the lakes in the model by the variability observed over all the years of the mass balances) indicates that the isotopic signature of the lake sediment could change by up to 2.5‰. This isotope change is large enough to account for the historical δ¹³C changes observed in the δ¹³C sediment record, suggesting that allochthonous DOC can drive the sediment record.