Different aspects of natural organic matter composition and cycling have been studied using solid-state 13C and 31P Nuclear Magnetic Resonance (NMR) spectroscopy. Depending on the specific study, complementary analytical techniques such as elemental, isotopic and molecular analyses have also been applied. Samples from a variety of environments were examined including ocean waters, marine sediments and atmospheric aerosols. Studies from all these environments illustrate differences in natural organic matter composition resulting from various factors such as sources, cycling mechanisms and redox conditions. In the marine water column, organic matter of two different size fractions (dissolved and particulate) is found to have distinctly different bulk chemical and isotopic compositions. Overall, this indicates that particulate organic matter does not form from the simple physical aggregation of dissolved organic matter, and dissolved organic matter is not the primary source for particulate organic matter. Comparison of carbon and phosphorus compositional changes with depth in the ocean within the dissolved and particulate fractions reveals differences in cycling mechanisms. In the marine water column, selective mineralization of specific carbon compounds such as carbohydrates and amino acids occurs relative other species such as lipids. Whereas for phosphorus, the relative proportion of the different functional groups are unvarying with depth. In marine sediments, NMR spectroscopy reveals P cycling for specific phases such as polyphosphates is a function of sediment redox conditions. In atmospheric aerosols 13C NMR spectroscopy shows differences in water-soluble organic carbon composition from urban versus biomass burning sources. Urban aerosols have higher aliphatic and lower aromatic compound contents relative to samples derived from biomass burning. The results of these studies provide new insights into carbon and phosphorus cycling in the environment and demonstrate the capabilities of solid-state NMR as a tool for investigating natural organic matter composition.

Woody invasion into grasslands has been reported world-wide and has affected both the magnitude and spatial heterogeneity of soil carbon (C) and nitrogen (N). Since grasslands cover a large portion of the Earth's land surface, invasion of woody plants could have impacts on regional and global biogeochemistry. To understand large-scale ecological and policy implications of woody invasion, it is critical to understand the spatial pattern and uncertainty of soil C and N and their relationship with vegetation and soil attributes, as well as develop effective approaches to estimate soil C and N over large landscapes and regions. The goal of this study was to improve our understanding of the spatial pattern of soil organic carbon (SOC) and total nitrogen (TN) and their controlling factors in savanna landscapes and develop efficient sampling strategies for evaluating the effects of woody invasion. Specific objectives of this study were to: (1) Quantify the spatial pattern and uncertainty associated with SOC and develop efficient sampling strategies to estimate SOC storage; (2) Assess the influence of soil and vegetation factors on spatial distribution of SOC and TN; and (3) Determine the influence of physical variables related to landscape position and soil on woody vegetation structure. Conditional sequential indicator simulations indicated that woody encroachment into grassland increased both spatial heterogeneity and uncertainty of SOC, which increased errors in estimating SOC storage. Stratified random sampling with higher density in woody patches, plus structured sampling in cluster with strong spatial pattern, substantially increased estimation accuracy. Efficient sampling strategies for estimating SOC storage were developed based on these findings. Direct and spatial correlation and scaling analyses showed that SOC and TN were strongly correlated with litter and root biomass. Invaded woody vegetation has the most impact on spatial distribution of SOC and TN. Canonical correspondence analysis showed that variables related to landscape position were the primary factors determining the spatial distribution of woody species. These new insights will facilitate the estimation of soil C and N pools at landscape and regional scales, and will help evaluate the potential impacts of woody plant encroachment on the biogeochemistry of C and N.

Soil hydraulic properties, such as saturated hydraulic conductivity (Ks), have high spatial variation, but little is known about how to vary a few measurements of Ks over an area to model hydrology in a watershed with complex topography and multiple land uses. Variations in soil structure, macropores (especially in soil that shrink and swell), land use, and soil development can cause large variations in Ks within one soil type. Characterizing the impacts of soil properties that might vary systematically with land use and terrain attributes on Ks rates would provide insight on how management and human activity affect local and regional hydrology. The overall objective of this research was to develop a strategy for using published infiltration and Ks measurements by the Natural Resources Conservation Service for watershed hydrology applications in a Vertisol, and to extend this knowledge toward developing recommendations for future infiltration measurements. To achieve this goal, soil infiltration measurements were collected across three catenas of Houston Black and Heiden clays (fine, smectitic, thermic Udic Haplusterts) under three land uses (improved pasture, native prairie, and conventional tillage row crop). Measurement locations were selected to account for variation in terrain attributes. Overall, Ks values were not significantly different across different landscape positions; however, in fields under similar land uses, Ks values were found to be lower in the footslope positions and higher in the backslope positions. The pedotransfer function, ROSETTA, provided estimates of 64 percent of the overall variability in Ks while also providing accurate estimates of the mean of Ks when particle size distribution and bulk density are used as inputs in the model. Through the use of multiple regression analysis, soil antecedent water content, bulk density, clay content, and soil organic carbon along with two indicator variables for the catenas were highly correlated (r2 = 0.59) with Ks. The indicator variables explained 17 percent of the variation in Ks that could not be explained by measured soil properties. It is recommended that when NRCS measures Ks on benchmark soils, especially high clay soils, that they collect particle size distribution, bulk density, organic carbon, and antecedent water content data.

Environmental indicators were developed and evaluated to assess the impact of mobile sources on emissions, air quality, exposure and health. Different levels of indicators are discussed, from single species to multipollutant indicators. Carbon monoxide (CO), Nitrogen oxides (NOx) and elemental carbon (EC) were chosen as indicators of mobile sources because emissions of these pollutants are largely attributed to mobile sources and ambient concentrations have a close response to the change in mobile source emissions. These pollutants were used in the construction of the integrated mobile source indicators (IMSI). The IMSI have larger spatial representativeness and stronger associations with cardiovascular diseases (CVD) than single pollutants. The use of IMSI in epidemiologic modeling constitutes an alternative approach to assess the health impact of pollutant mixtures and can provide support for the setting of multipollutant air quality standards. The human health benefits of reducing mobile sources emissions were more consistent using multipollutant indicators. Indicator values and uncertainties, in the form of indicator sets, are presented with their associated outcomes and attributes to be useful for policy makers who are interested not only in the value of the indicators, but also in their associated uncertainties and their applicability at other times and other regions.

I denna rapport undersöks hur mängden organiskt kol, TOC (Totalt organiskt kol), varierar i tid och rum i Mälarens avrinningsområde, samt vad det är som styr TOC-halten i Mälaren. Det är viktigt att förstå dynamiken hos TOC i Mälaren och i dess avrinningsområde eftersom ökat TOC i vattnet påverkar vattenkvaliteten och orsakar problem vid beredning av dricksvatten. TOC kan bland annat reagera med klor/UV-ljus och bilda cancerframkallande ämnen. Det kan också öka antal mikrober i vattnets distributionssystem. Arbetet omfattar analys av samband mellan elementen, transportberäkningar per ytenhet av elementen till Mälaren och en modelleringsansats för ett av avrinningsområdena. Rapporten innehåller även en jämförelse mellan de olika vattenföringsmodellerna samt uppmätt vattenföring för analys av eventuella systematiska skillnader mellan dessa som påverkar beräkningen av TOC och de andra elementens transport till Mälaren. Analysen av sambanden mellan variablerna TOC (mg/l), kaliumpermanganat förbrukning (KMnO4, mg/l), absorbans_F (F=filtrerad), järn (mg/l), mangan (mg/l) och SO4_IC (sulfat mätt med hjälp av jonkromatografi, mg/l), visade att vissa av dessa variabler är korrelerade med varandra. TOC mot KMnO4 och TOC mot absorbans_F hade de bästa anpassningarna med respektive R2- värden 0,65 och 0,59 och p-värden <0,001. Årsnederbörd är positivt korrelerad med TOC per ytenhet för Kolbäcksån med R2-värde 0,63 och p-värde <0,01, vilket innebär att sambandet är signifikant. Ökad årsnederbörd leder till ökad tillförsel av TOC till Mälaren. Det finns däremot inget signifikant samband mellan TOC-transport per ytenhet och årsmedeltemperatur. Arealflödesberäkningar tyder på att den största tillförseln av TOC- transport per ytenhet kommer från den nordöstra delen av Mälaren. Fyrisån står för den största tillförseln av TOC. Hydrologiska, kemiska och meteorologiska data inkluderades i modeller för att kunna skatta TOC-halten i Mälaren. Temperatur-, evapotranspirations- och nederbördsdata användes i en hydrologisk modell, HBV- modellen, för att simulera vattenföringen från avrinningsområdet. Sedan användes en processbaserad modell, INCA- C, som drivs av hydrologisk data och beräknade grundvattenbildning och markfuktighet för att simulera tidsmässiga mönster i TOC. Invariablerna till INCA-modellen, markfuktigheten och HER (grundvattenbildning), simulerades med hjälp av HBV- modellen. Dessa modeller tillämpades i Kolbäcksån (ett av Mälarens största avrinningsområden). Modelleringen av Kolbäcksåns TOC- halt resulterade i en modell som anpassade dynamiken mellan 1996 och 2009, men missar den mellan 2009 och juni 2010, med bäst anpassning mellan 2006 och 2008. R2- och NS värden som erhölls för modellen var 0,086 och -0,059. / In this report, it has been investigated how the amount of organic carbon, TOC, varies in time and space in the basin of Mälaren, and what controls the TOC content in the lake. It is important to understand the dynamics of the TOC in the lake and its catchment because increased TOC in the water affects water quality and causes problems in the preparation of drinking water. Particularly, it can react with chlorine / UV- light and form carcinogenic substances. It can also increase the number of microbes in water distribution systems. In addition the work includes analysis of the relation between water chemistry variables, annual fluxes calculations (g/m2/year) of element flows to the lake and a modeling approach to a watershed. Annual fluxes calculations (g/m2/year) indicate that the largest supply of TOC to the lake comes from the northeast of the lake. Fyrisån accounts for the largest input of TOC to the lake. The high TOC-flux is due to a small proportion of open water in the catchment. Hydrological, chemical and meteorological data have been included in models to estimate the TOC content in the Mälaren. Input data processing, especially precipitation data, has been an important part of the work as it affects the whole model. Temperature, evapotranspiration and precipitation data were used in a hydrological model, HBV model, to simulate the flow from the catchment area. Then a process-based model, INCA-C, operated by the hydrological data and soil moisture, has been used to simulate the temporal patterns in TOC. The input variables to INCA-C- model, soil moisture and HER (Hydrological effective rainfall), have been simulated using the HBV- model. Those models were applied in Kolbäcksån, one of the lake's largest catchments. The modeling of Kolbäcksån resulted in a model that captured the dynamics of a few periods of the whole time series. The modeling of Kolbäcksån TOC-concentration resulted in a model that captured the dynamics between 1996 and 2009, but misses it between 2009 and June 2010. R2 and NS values obtained for the model were 0.086 and -0.059, respectively.

The aim of this dissertation was to understand lithogenic suspended sediment transport mechanisms and distribution in two river-influenced margins: The Cariaco Basin, Venezuela, and the Amazon Shelf, Brazil. Lithogenic sediment input in the Cariaco Basin is controlled by small mountainous rivers (SMR), while in the Amazon Shelf it is dominated by the Amazon River, the largest river in the world in terms of freshwater discharge (~20% of global riverine discharge). Optical transmissometer measurements were coupled with particulate organic matter (POM) observations to understand changes in the geochemical composition of suspended sediment and spatial/temporal distributions over the two regions of interest. In the Cariaco Basin sampling was conducted during the rainy seasons of September 2003, 2006 and 2008, and during the upwelling period (dry season) of 2009. Our results suggest that bottom nepheloid layers (BNL) originating at the mouth of the SMR discharging into the Cariaco Basin are a major delivery mechanism of terrigenous sediments to the basin's interior year-round. Intermediate nepheloid layers (INL) were also observed near the shelf break (~100m) and appear to effectively carry terrigenous material laterally from the shelf to deep waters, thereby providing a plausible supply mechanism of the terrestrial material observed in sediment traps, deployed >70 km offshore as part of the CARIACO Ocean Time-Series. These findings highlight the importance of small, local rivers in the Cariaco Basin as sources of terrestrial material. Indeed, the low isotopic composition of particulate organic carbon (δ13Corg, ~-30 - -24 ‰) carried by the BNL suggests that this material was continentally derived. BNL δ13Corg also changed with season, indicating that the geochemical composition of BNL reflects particle source. These nepheloid layers contained relatively low POM concentrations (average of 10%), agreeing well with published data, yet the fine sediment of the BNL may serve as mineral ballast, enhancing the sinking velocities of POC and thus increasing the efficiency of the biological pump in Cariaco. We suggest that during the transition between the upwelling and rainy season BNL deliver sediment to the deep Cariaco Basin in pulses. During upwelling, BNL are retained on the inner shelf by onshore Ekman transport associated with upwelling. The nepheloid layers are later released as the upwelling subsides; this, coupled with high river discharge rates, may explain the seasonal pulse of sediment observed at the end of the upwelling period (May) in the sediment trap array. The SMR in Cariaco also have the capacity to deliver large amounts of sediment to the Cariaco Basin during episodic events, such as earthquakes and floods. During September 2008 a sediment density flow was observed in the eastern Cariaco Basin, likely triggered by a magnitude 5.2 earthquake that occurred on August 11, 2008 off the city of Cumaná. Elevated suspended sediments near the bottom were observed at the mouth of the Manzanares Canyon (> 90 g m-2, over a depth of 165 m) and decreased to ~11 g m-2 (over a depth of 40 m) 42 Km away from the canyon's mouth at the CARIACO Ocean Time-Series site (10.5° N, 64.67° W). The sediment flux associated with this single event was ~ 10% of the total annual sediment flux that typically reaches the Cariaco Basin deep seafloor. Average carbon to nitrogen atomic ratios (C/N) as well as C and N isotopic composition confirm that most of the organic matter transferred by the sediment flow was of continental origin (C/N ratios of ~19.3, δ13C of -27.04 ‰, and δ15N of 6.83 ‰). The Manzanares River mouth is located at the head of the canyon, and likely supplies most of the fine grained sediments and fresh organic carbon that accumulate in the upper part of the canyon. This suggests that the canyon is an active depositional center, and its proximity to the Manzanares River and Cariaco Basin is critical for sediment supply offshore, which in turn can have a significant impact on the long-term sequestration of carbon into the deep basin. The nutrient and sediment biogeochemistry of the outer Amazon Shelf was studied in February-March 2010 to replicate observations made by the AmasSeds study in 1989-1991. These transects roughly corresponded to the AmasSeds Open Shelf (OS) and River Mouth (RM) transects. Onshore winds (~6 m s-1) contained the Amazon plume within ~120 Km of the coast; the plume was visible only in the mid-shelf stations located closest to the coast in the OS transect. Within the river plume, surface dissolved inorganic nutrient concentrations were near zero, except for silicates (4-6 μM). Coupled with oxygen supersaturation (AOU < 1), this suggested complete biological uptake of the major dissolved inorganic nutrients (N, P). Dissolved organic carbon (DOC) was also highest within the plume (average of 116 μM), decreasing to ~73 μM in oceanic waters. Total suspended solids (TSS) in surface waters within the plume were ~1-1.5 mg l-1, decreasing to ~0.2-0.3 mg l-1 in all other sampled stations both over the shelf and in deeper waters. TSS were highest within BNL (22-33 mg l-1) observed over the inner shelf; BNL were not observed outside the area of the Amazon plume. Suspended particulate organic carbon (POCsusp) showed a depleted δ13C isotopic signal (~-25 ‰ to -28 ‰) in surface and bottom waters, suggesting terrestrial provenance. Within the BNL, %POC was low (0.6-0.9%, as compared to 7-18% in surface waters), showing extensive and rapid decomposition of organic matter over the shelf. Atomic C/N ratios in particulate organic matter both in surface waters and within BNL were relatively close to Redfield's (8-14) and relatively stable over the area sampled. Particulate atomic organic carbon vs. particulate organic phosphorous (POC/POP) ratios were also low within the BNL (~110) and increased offshore (>500), suggesting a direct input of particulate P from the Amazon River or from reworked surface sediments. The fraction of POC in surface sediments was also low (0.73 ±; 0.56%; N = 5) and relatively uniform across the region sampled. We estimated instantaneous fluxes of 38.7 metric tons TSS s-1, 0.24 metric tons POC s-1 and 6.42 x 10-3 metric tons POP s-1 northwestward over an area extending between ~50 Km and 120 Km offshore. Our TSS estimates are 30% lower than those calculated by Nittrouer et al. (1986) during peak discharge of the Amazon. We also calculated that some 1.50 Tg yr-1 of DOC were being flushed northwestward along the outer shelf annually, which represent ~6% of the total DOC transported by the Amazon. By analyzing these two geographical settings it was possible to compare and contrast transport mechanisms of continentally-derived material and establish the relative importance of each mechanism in their different environment. There is still much to be understood regarding BNL in the Cariaco Basin, such as their role within the Manzanares Submarine Canyon with regards to sediment contribution and deposition. Additionally, during the last 30 years, anthropogenic influences on the small rivers around the Basin have significantly altered the drainage and sediment loads, yet reliable data to quantify the level of influence and change over time are not available. We need a better understanding of the natural variability of these small, tropical fluvial systems, trends and impact of episodic events, to better interpret the climate record stored at the bottom of the basin and predict future ecosystem changes in the region. In the Amazon Shelf, more accurate estimates of DOC, POC and POP fluxes northwestward are warranted. The magnitude of the Amazon River discharge dampens changes that have occurred in the last 20 years within the Amazon Basin, suggesting that historic Amazon Shelf sediment and carbon estimates are still valid. The data presented here adds to the growing body of literature that highlights the significance of river-influenced continental margins as sites of organic carbon deposition, remineralization export and sequestration.

Records of change of [delta]13C values in vertebrate teeth offer an opportunity to gain insight into changes in past vegetation. Increasingly, teeth from small mammals are used for such purposes, but because their teeth grow very rapidly, seasonal changes in vegetation potentially provide a large source of variability in carbon isotope composition, complicating interpretations of small mammal tooth isotope data. To investigate the controls of seasonality on the stable isotope composition of fossil teeth, we constructed a Monte-Carlo-based model to simulate the effects of changes in the seasonal pattern of diet in leporid lagomorphs (rabbits and hares) on the distribution of [delta]¹³C values in random populations of leporid teeth from the Edwards Plateau in central Texas. Changes in mean-state, seasonal vegetation range, and relative season length manifest themselves in predictable ways in the median, standard deviation, and skewness of simulated tooth [delta]¹³C populations, provided sufficient numbers of teeth are analyzed. This Monte Carlo model was applied to the interpretation of a 20,000 year record of leporid tooth [delta]¹³C values from Hall's Cave on the Edwards Plateau in central Texas. Variations in the [delta]¹³C values of teeth deposited at the same time (standard deviation = 1.69%) are larger than changes in the mean vegetation composition reconstructed from bulk organic carbon [delta]¹³C, indicating the influence of short-term variability, making it difficult to assess changes in mean C3/C4 vegetation from the tooth [delta]¹³C data. However, populations of teeth from different climate intervals (e.g., the late Glacial, Younger Dryas, and the Holocene) display changes in the shape of the tooth [delta]¹³C distributions. Interpretation of these changes as shifts in seasonal vegetation patterns that are based upon results from our model are consistent with hypothesized climatic changes. An increase in the standard deviation of the tooth population between the late Glacial and the Younger Dryas -- Holocene is consistent with an increase in seasonality. Furthermore, a shift to more C3-dominated vegetation in the tooth [delta]¹³C distribution during the Younger Dryas is accompanied by a more skewed population -- indicative of not only wetter conditions but an increase in the duration in the C3 growing season. However, late Holocene changes in vegetation are not clear in the tooth data, despite the evidence from bulk organic carbon [delta]¹³C values for an increase in % C3 vegetation of 57%. Small mammal teeth can potentially provide unique insights into climate and vegetation on seasonal and longer timescales that complement other data, but should be interpreted with a careful consideration of local conditions, taxon ecology and physiology, and the dominant timescales of isotope variability. / text

High concentrations and fluxes of dissolved organic carbon (DOC) in fluvial systems are associated with the dark brown water colour familiar in many upland, peat-dominated areas and may indicate a depletion of the terrestrial carbon store. The removal of this colour can also be problematic and expensive for water companies as well as affecting the ecological functioning of the water body through factors such as reduced light penetration through the water column. Disturbance resulting from activities such as land use change can also enhance the loss of carbon and this may manifest itself in elevated concentrations and fluxes of DOC from aquatic systems. This thesis describes and explains patterns of change in DOC quantity and quality from the Crosswater, Crosswater of Luce and Tig catchments draining Arecleoch Forest, a peatland in south Ayrshire, Scotland, from 2008 to 2010. This time period incorporates the installation of a 60-turbine wind farm built and operated by Scottish Power Renewables (SPR). Water samples were collected from Arecleoch at different spatial scales ranging from catchments to soil pore water and temporal scales ranging from daily to seasonally. Concentrations of DOC were measured and fluxes estimated at the catchment scale. DOC concentrations from all three catchments exhibited the well-established seasonal pattern with maxima in late August/early September and minima seen in February/March. The Tig catchment experienced the greatest burden of disturbance from the wind farm development and returned the highest DOC concentrations and fluxes. The Crosswater catchment, used as a control site due to its isolation from wind farm activities, had higher DOC concentrations than the Crosswater of Luce throughout the monitoring period possibly due to a greater proportion of forest cover. ii DOC flux ranged from 35.0 g C m-2 yr-1 from the Crosswater of Luce catchment in 2008 to 55.0 g C m-2 yr-1 from the Crosswater in 2009. The Tig catchment was not monitored for the whole period but returned the highest DOC fluxes of the three catchments between January and June 2010 (15.7 g C m-2). These values are considered high for UK peatlands. It is possible to make a tentative estimate of an extra 12 g C m-2 being exported from the Crosswater of Luce in 2009 that may have been a result of wind farm and/or forestry activities in the catchment. At the sub-catchment scale, “hot spots” of high DOC concentrations (up to 113.4 mg L-1) were found during the final survey of headwater streams inside the development area of the wind farm site during construction in August 2010. Further surveys are recommended to assess whether DOC concentrations have decreased since completion of the wind farm. Daily water samples were collected upstream and downstream of turbine 33 during the excavation of the turbine base. DOC concentrations were higher downstream before work began on the turbine base and although the gap between upstream and downstream DOC concentrations increased over the monitoring period, statistical comparisons of these differences before and after the start of excavation work were not significant at the 95 % confidence level. Challenges arose from the practicability of conducting robust research on a construction site and novel approaches to monitoring DOC were developed. Activity scores were used to quantify the effect of peatland disturbance on DOC concentrations at the catchment scale. The results suggest that this approach may have merit but requires comprehensive site records from the developer. The non-linear nature of the individual wind farm development and forestry activities made it impractical to disentangle the impact of each, particularly for forest harvesting. iii Activity scores could, together with other information gathered from site records, be useful to developers as an indicator of the most likely periods for peat disturbance. Knowledge of the differing disturbance potential of the various activities could also provide useful information to feed into the carbon payback calculator. DOC quality was explored using ultraviolet (UV) absorbance, specific UV absorbance (SUVA) and E4/E6 ratios. The latter metric identified changes in the composition of DOC related to disturbance with water samples from areas draining land subject to disturbance having lower E4/E6 ratios indicating a greater degree of humification of the DOC. This research provides one of only three studies to investigate concentrations and fluxes of DOC in water courses draining land subject to disturbance relating to wind farm construction. It is the only study that incorporates a period of time prior to work beginning and takes in the whole of the development phase. In this respect it provides a valuable addition to our understanding of the way in which peatlands respond to land use change and may provide useful tools to assist developers in minimising the impact of their activities on these valuable carbon stores.

From the Proceedings of the 1975 Meetings of the Arizona Section - American Water Resources Assn. and the Hydrology Section - Arizona Academy of Science - April 11-12, 1975, Tempe, Arizona / Denitrification is the only reaction capable of removing the tremendous quantity of nitrogen applied when high-rate land filtration systems are used for renovating sewage water. This study determined that a shortage of organic carbon limits denitrification, and the effects of increased dissolved organic carbon concentrations on soil clogging and movement of fecal coliform bacteria are clearly shown. Finally, the removal of dissolved organic carbon at different carbon concentrations during high rate soil filtration (40-50 cm/day) also limits denitrification.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal