The pollutant load in road runoff is related to traffic densities and road maintenance activities. Inurbanised areas treatment of road runoff is common and often considered necessary. The pollutantsare partitioned between the particulate and dissolved matter. However, the contaminantstend to have an affinity to the particulate material. Sedimentation, the predominant treatmentmethod for road runoff uses various types of ponds. Design tools used for stormwater treatmentsystems are based on extensive data from existing treatment systems. The variations in the empiricaldata make it difficult when attempting to evaluate precise conditions for pollutant removaland thereby minimising the land use for a treatment facility. This is a concern in highly urbanisedareas where land use often is restricted.In this work, field studies were conducted in three separate watersheds along the same motorwaywith an annual average daily traffic exceeding 120,000 vehicles. The aim was to assess treatmentconditions for the removal of contaminants from road runoff.The study of mass transport of total suspended solids used the EU Directive (1991/271/EEC)discharge requirement for urban wastewater treatment: 60 mg/l during winter and summer. Theresults showed that a capture of the total runoff volume was necessary during both seasons. Tenmetals (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), as dissolved and particulate bound, werestudied in the road runoff during a winter season and the following summer period. The dissolvedpart of Al, Cd, Co, Cr, Mn, and Ni was significantly higher in winter. The mass concentration(mg/kg) for all metals was significantly higher over the summer except for Al and Co, whichshowed a higher mass concentration during the winter. The total metal concentration showed agood correlation to total suspended solids (TSS) during winter with exception for Cd. Good correlationto TSS was also found for the summer period for Al, Cu, Fe, Mn, Ni, and Zn. A simplemodel could describe sedimentation by the initial concentration of TSS, albeit road salt (NaCl)had a significant impact on the sedimentation process during winter. Removal of dissolved metalswas studied by column experiments using water granulated blast furnace slag. The result showedgood removal for Cd, Cu, Ni, and Zn independent of NaCl concentrations. Sediment accumulation(mg sediment/mm precipitation) was relatively consistent for the studied summer seasons asopposed to winter. The sediment differed in metal mass concentrations (mg/kg) between theseasons. Concentrations of Cu and Zn were high in regard to the guidelines for sensitivity ofsediment dwelling organisms and Swedish guidelines for contaminated soils.The findings suggest that the entire runoff volume must be captured for treatment. The reductionof TSS concentration could be estimated for a specific surface load (m/h). This would alsoapply for majority of the studied metals that correlated well to the particulate material. Reactivefilter technology using water granulated blast furnace slag could be applied for treatment of runofffor the reduction of dissolved metals. However, long-term studies are necessary for its practicalimplementation. Furthermore; the work shows that on-line turbidity measurements could beused for expedient process control for treatment facilities in similar watersheds dominated byroads. The work could be used together with existing design methods and models to evaluate andoptimise road runoff treatment. / Föroreningsbelastningen i vägdagvatten är beroende av trafikbelastningen och vägunderhållet. Iurbaniserade områden är behandling av dagvatten vanlig och ofta bedömd nödvändig. Föroreningarnaär lösta och partikulära, men har vanligen en affinitet till det partikulära materialet. Denförhärskande behandlingsmetoden för dagvatten är sedimentering, vanligen i dammar. Designmodellernabygger på data från olika befintliga dagvattenanläggningar. Det varierande ursprungettill det empiriska underlaget medför svårighet att precist värdera designförutsättningarna och såledesminimera behandlingsanläggningens storlek. I förtätad stadsmiljö, där tillgång på mark ärbegränsad, kan detta vara ett problem.I detta arbete har fältförsök genomförts i tre avrinningsområden vilka domineras av en motorledmed en årlig dygnstrafik större än 120,000 fordon för att utvärdera behandlingsförutsättningar förvägdagvatten.Masstransporten av suspenderat material (SS) utvärderades utifrån EU Direktivet(1991/271/EEC) och gränsvärdet för avloppsvatten på 60 mg/l under vinter och sommar. Studienvisade att hela avrinningsvolymen bör behandlas oberoende av säsong. Fördelningen mellanpartikulärt och löst material studerades för tio metaller (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn)under vinter och sommar. Den lösta delen av Al, Cd, Co, Cr, Mn och Ni var signifikant högreunder vintern. Den partikulära koncentrationen (mg/kg) för samtliga metaller var högre undersommaren med undantag för Al och Co vilka förekom i högre halter under vintern. Totalhalten(μg/l) av metallerna korrelerade väl med SS under vintern med undantag för Cd. Likaledes uppvisaderesultaten en god korrelation mellan SS och Al, Cu, Fe, Mn, Ni och Zn under sommaren.Sedimenteringsegenskaperna kunde beskrivas med en enkel modell utifrån koncentration av SS,men förhöjda halter av vägsalt (NaCl) befanns påverka sedimenteringen under vintern. Reduktionav lösta metaller studerades i pilotförsök med vattenkyld granulerad masugnsslagg. God avskiljningerhölls för Cd, Cu, Ni och Zn oberoende av förhöjda halter av vägsalt. Ackumulering avsediment (mg sediment/mm nederbörd) befanns vara konstant under sommaren i motsats tillstuderade vinterperioder. Sedimentkoncentrationerna av Cu och Zn var förhöjda med avseendepå riktlinjer för känslighet hos sedimentlevande organismer samt för återanvändning av slam.Resultaten visar att hela avrinningsvolymen måste behandlas. Reduktion av SS samt huvuddelenav metallerna, vilka visade god korrelation till det partikulära materialet, kan skattas utifrån enspecifik ytbelastning (m/h). Reduktion av lösta metaller kan ske med granulerad masugnsslagg,dock bör långtidsstudier genomföras. Vidare visar studien på möjligheten att nyttja kontinuerligturbiditetsmätning för en effektiv och praktisk processkontroll i reningsanläggningar för liknandeavrinningsområden med hög trafikbelastning. Resultaten av arbetet kan användas för bedömningoch optimering av vägdagvattenbehandling tillsammans med existerande designmetoder och modeller. / QC 20100709

Background: Ambient air pollution is associated with adverse health effects, but the sources and components, which cause these effects is still incompletely understood. The aim of this thesis was to investigate the pulmonary effects of a variety of common air pollutants, including diesel exhaust, biomass smoke, and road tunnel and subway station environments. Healthy non-smoking volunteers were exposed in random order to the specific air pollutants and air/control, during intermittent exercise, followed by bronchoscopy. Methods and results: In study I, exposures were performed with diesel exhaust (DE) generated at transient engine load and air for 1 hour with bronchoscopy at 6 hours post-exposure. Immunohistochemical analyses of bronchial mucosal biopsies showed that DE exposure significantly increased the endothelial adhesion molecule expression of p-selectin and VCAM-1, together with increased bronchoalveolar lavage (BAL) eosinophils. In study II, the subjects were exposed for 1 hour to DE generated during idling with bronchoscopy at 6 hours. The bronchial mucosal biopsies showed significant increases in neutrophils, mast cells and lymphocytes together with bronchial wash neutrophils. Additionally, DE exposure significantly increased the nuclear translocation of the aryl hydrocarbon receptor (AhR) and phosphorylated c-jun in the bronchial epithelium. In contrast, the phase II enzyme NAD(P)H-quinone oxidoreductase 1 (NQO1) decreased after DE. In study III, the 2-hour exposures took place in a road tunnel with bronchoscopy 14 hours later. The road tunnel exposure significantly increased the total numbers of lymphocytes and alveolar macrophages in BAL, whereas NK cell and CD56+/T cell numbers significantly decreased. Additionally, the nuclear expression of phosphorylated c-jun in the bronchial epithelium was significantly increased after road tunnel exposure. In study IV, the subjects were exposed to metal-rich particulate aerosol for 2 hours at a subway station with bronchial biopsy and BAL sampling at 14 hours. The subway exposure significantly increased the concentration of glutathione disulphide (GSSG) in BAL, with no airway inflammatory responses. In contrast, the number of neutrophils in the bronchial mucosa and the nuclear expression of phosphorylated c-jun in the bronchial epithelium tended to decrease after the subway exposure. In study V, the exposure to biomass smoke lasted 3 hours. Bronchoscopy was conducted 24 hours post exposure. The investigated biomass combustion emissions resulted in a significant increase in total glutathione and reduced glutathione in BAL, without any evident acute airway inflammatory responses.     Conclusion: The present thesis presents data from exposures of healthy subjects to a variety of common air pollutants, as compared with an air reference. Oxidative as well as bronchial mucosal and bronchoalveolar responses differed between these air pollutants, with the most pronounced airway effects seen after exposure to diesel exhaust. This may be due to differences in pulmonary deposition, physicochemical characteristics, toxicological pathways and potency. Additional studies will assist in addressing dose-response and time kinetic aspects of the airway responses.

No description available.

El impacto de la contaminación del aire es un tema crítico para el medioambiente y el clima. Una mala calidad del aire es un tema de importancia para la salud pública, especialmente en ambientes urbanos. El material particulado (PM), el ozono (O3) y el dióxido de nitrógeno (NO2) son los contaminantes más problemáticos en Europa y España. La Comisión Europea ha mostrado una gran preocupación por desarrollar técnicas que permitan incrementar el conocimiento sobre la dinámica de los contaminantes atmosféricos para asegurar el cumplimiento de la legislación y para informar a la población acerca de sus niveles. Además, la directiva europea 2008/50/CE establece la posibilidad de usar técnicas de modelización para informar sobre calidad del aire. Esta tesis doctoral está desarrollada en el marco de dos proyectos: El proyecto CALIOPE y el proyecto CICYT CGL2006-08903, ambos basados en la necesidad de desarrollar un sistema de calidad del aire que permita informar y entender los niveles de contaminación en Europa y España, con el objetivo de obtener un preciso pronóstico de la calidad del aire. Con ese propósito, el sistema de modelización CALIOPE se ha desarrollado con alta resolución espacial y temporal sobre Europa (12 km x 12 km y 15 capas, 1 hora), dominio madre, y España (4 km x 4 km y 15 capas, 1 hora), dominio anidado. CALIOPE consiste en un conjunto de modelos que tienen en cuenta la contaminación tanto antropogénica como natural. La disponibilidad del supercomputador MareNostrum, alojado en el Barcelona Supercomputer Center- Centro Nacional de Supercomputación, ha permitido trabajar a tan alta resolución. El objetivo principal de esta tesis es aumentar la confianza científica en el sistema CALIOPE, identificando sus puntos fuertes y débiles con un nivel de detalle que contribuya a establecer necesidades de mejora en el proceso de modelización. Por tanto, el presente trabajo ha evaluado espacial y temporalmente las simulaciones de calidad del aire sobre Europa y España en términos de O3, NO2, SO2, PM2.5 y PM10 en superficie sobre el año completo 2004. Para identificar el origen de las incertidumbres en la modelización del PM, su composición química ha sido también evaluada en ambos dominios. Las evaluaciones han sido realizadas sobre más de 150 estaciones de calidad del aire (más de 2 millones de datos experimentales). Además, esta tesis ha usado el sistema CALIOPE para analizar los patrones de calidad del aire sobre 2004, identificando claramente las áreas de contaminación. Las ideas más importantes que se desprenden de esta tesis son tres. Primero, las condiciones de contorno químicas basadas en un modelo global, como el LMDz-INCA2, son esenciales para modelizar el O3 troposférico sobre los dominios de estudio. Segundo, para simular la concentración de PM en el sur de Europa, tanto a escala rural como urbana, la contribución de polvo procedente del desierto del Sahara deber ser considerada debido a la proximidad al continente africano. La contribución del polvo del desierto a través del modelo BSC-DREAM8b ayuda satisfactoriamente a modelizar los picos de PM10 observados. Tercero, para ser capaz de modelizar la calidad del aire a escala urbana sobre España es esencial (1) una alta resolución espacial y temporal que permita describir fenómenos mesoescalares en áreas de topografía compleja , (2) un modelo de emisiones altamente desagregado como HERMES; (3) unos modelos que representen el estado actual del conocimiento en meteorología y química atmosférica / The impact of air pollution is a critical topic in environment and climate. Poor air quality is an important public health issue, especially in urban environments. Particulate matter (PM), tropospheric ozone (O3) and nitrogen dioxide (NO2) are the main problematic pollutants in Europe and Spain. The European Commission has shown a great concern for developing actions that allow increasing the knowledge on dynamics of atmospheric pollutants to assure the accomplishment of legislation and to inform the population about their levels. The European directive 2008/50/EC establishes the possibility of using modelling techniques to assess air quality. This Ph.D. thesis is developed in the framework of two projects: the CALIOPE project and the CGL2006-08903 CICYT project, both based on the necessity to develop an air quality modelling system that allows assessing and understanding the air pollution levels in Europe and Spain, with the aim of obtaining a precise air quality forecast. For that purpose, the CALIOPE air quality modelling system has been developed with high spatial and temporal resolution over Europe (12 km x 12 km, 1 h), as a mother domain; and Spain (4 km x 4 km, 1 h), as the nested domain. The CALIOPE system consists in a set of models that take into account both anthropogenic and natural pollution. The availability of the MareNostrum supercomputer, held in Barcelona Supercomputing Center- Centro Nacional de Supercomputación, has allowed such configuration of the CALIOPE system. The main objective of the present Ph.D. thesis is to increase the scientific confidence on the CALIOPE system, identifying skills and weakness with a degree of detail that contributes to establish necessities of improvements in the modelling process. Therefore, the present work has spatially and temporally evaluated CALIOPE air quality simulations over Europe and Spain in terms of O3, NO2, SO2, PM2.5, PM10 concentrations over the full year 2004. In order to identify the origin of uncertainties in PM modelling, PM chemical composition has been also evaluated in both target domains. Evaluations have been performed across more than 150 air quality-monitoring stations and over more than 2 million of experimental data. Furthermore, this Ph.D. thesis has used the CALIOPE system to assess air quality pattern over the year 2004, identifying clearly the areas of air pollution. There are three major thrusts of the present Ph.D. thesis. First, chemical boundary condition based on a global model, such as LMDz-INCA2, becomes essential to model O3 background concentrations in the target domains. Second, to simulate PM concentration in southern Europe, both regional and urban scales, the contribution of dust from the Saharan desert should be taken into account, since that region is frequently affected by dust outbreaks due to its proximity to the African continent. The contribution of desert dust through the BSC-DREAM8b helps to satisfactory model the observed episodic PM10 concentration peaks. Even more, the contribution of sea-salt aerosol is especially important over coastal areas. Third, to be able to model the air quality in urban scale over Spain it is essential (1) a high spatial (4 km x 4 km and 15 layers) and temporal (1h) resolution that allows describing mesoscale phenomena in very complex terrains; (2) a high disaggregated emission model to describe the sources, such as HERMES; and (3) an state-of-the-science meteorological and chemical models. This Ph.D. thesis has demonstrated that CALIOPE system applied over Europe and Spain is a useful tool which may contribute to (1) forecast air pollution in urban/suburban areas with a pervasive influence of anthropogenic emissions on a local scale and over very complex terrains and meteorology patterns; (2) assess about air pollution, discriminating between anthropogenic and natural episodes; and (3) manage air pollution, by means of modification of urban strategies or requirements of the legislation.

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.

Introduction: Despite the known consequences of cigarette smoking, almost 20% of adults in the United States smoke. Smoking has been shown to harm nearly every organ of the body. Its detrimental effects have been seen not only in smokers themselves but also in those exposed to secondhand smoke (SHS) at work and in other public places. Methodology: The purpose of this thesis was to examine compliance with the signage requirement of the Georgia Smokefree Air Act (GSAA) of 2005 among 99 hospitality venues located in Atlanta. Photographs of bars and restaurant entrances were taken and raters then classified each venue as compliant or non-compliant with smoking status signage requirements of the GSAA. Additionally, air samples were collected using Sidepak equipment from 59 venues in order to estimate the PM2.5 levels, which is a recognized measure of air quality. With Spearman’s rho correlation coefficient (r), analyses were run to determine correlations between signage compliance, number of cigarettes being smoked, and smoking permitted with air quality (PM2.5). Analyses were conducted using the Statistical Package for Social Sciences (SPSS) version 19. Results: Of the 99 venues assessed, only 21 (21.2 %) complied with the signage requirements of the GSAA. Venues that do adhere to signage requirements and indicate no smoking on their signs and at the same time via telephone stated that smoking is prohibited had the lowest PM2.5 levels =15.03. On the contrary, those venues that display signs permitting smoking and via telephone indicated smoking is allowed had the highest PM2.5 levels =230.31. It was determined that there is a strong positive correlation between PM2.5 and “number of cigarettes” (r=.611, n=59, p<.001) as well as moderate correlation between PM2.5 and “smoking permitted” as indicated from phone calls (r=.464, n=59, p<.001). However, analysis showed a weak correlation between PM2.5 and “signage compliance” in accordance with GSAA (r=.107, n=59, p>.001). Conclusions: Enforcement of GSAA must be enhanced in order to better protect workers and patrons of Atlanta’s bars and restaurants from harmful exposure to SHS. Findings from this study support that prohibiting smoking in bars and restaurants and having signs stating that smoking is prohibited would improve air quality and protect workers by eliminating their exposure to SHS while working.

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.

<p>In the first chapter of this dissertation, I outline a hedonic equilibrium model that explicitly controls for moving costs and forward-looking behavior. Hedonic equilibrium models allow researchers to recover willingness to pay for spatially delineated amenities by using the notion that individuals "vote with their feet." However, the hedonic literature and, more recently, the estimable Tiebout sorting model literature, has largely ignored both the costs associated with migration (financial and psychological), as well as the forward-looking behavior that individuals exercise in making location decisions. Each of these omissions could lead to biased estimates of willingness to pay. Building upon dynamic migration models from the labor literature, I estimate a fully dynamic model of individual migration at the national level. By employing a two-step estimation routine, I avoid the computational burden associated with the full recursive solution and can then include a richly-specified, realistic state space. With this model, I am able to perform non-market valuation exercises and learn about the spatial determinants of labor market outcomes in a dynamic setting. Including dynamics has a significant positive impact on the estimates of willingness to pay for air quality. In addition, I find that location-specific amenity values can explain important trends in observed migration patterns in the United States.</p><p>The second chapter of this dissertation describes a model which estimates willingness to pay for air quality using property value hedonics techniques. Since Rosen's seminal 1974 paper, property value hedonics has become commonplace in the non-market valuation of environmental amenities, despite a number of well-known methodological problems. In particular, recovery of the marginal willingness to pay function suffers from important endogeneity biases that are difficult to correct with instrumental variables procedures [Epple (1987)]. Bajari and Benkard (2005) propose a "preference inversion" procedure for recovering heterogeneous measures of marginal willingness to pay that avoids these problems. However, using cross-sectional data, their approach imposes unrealistic constraints on the elasticity of marginal willingness to pay. Following Bajari and Benkard's suggestion, I show how data describing repeat purchase decisions by individual home buyers can be used to relax these constraints. Using data on ozone pollution in the Bay Area of California, I find that endogeneity bias and flexibility in the shape of the marginal willingness to pay function are both important.</p><p>Finally, in the third chapter of this dissertation, I combine the insights of the Bajari-Benkard inversion approach employed in second chapter with more standard estimation techniques (i.e., Rosen (1974)) to arrive at a new hedonic methodology that allows for flexible and heterogeneous preferences while avoiding the endogeneity problems that plague the traditional Rosen two-stage model. Implementing this estimator using the Bay Area ozone data, I again find evidence of considerable heterogeneity and of endogeneity bias. In particular, I find that a one unit deterioration in air quality (measured in days in which ozone levels exceed the state standards) raises marginal willingness to pay by $145.18 per year. The canonical two-stage Rosen model finds, counter-intuitively, that this same change would reduce marginal willingness to pay by $94.24.</p> / Dissertation

The design of interface elements in geotechnical engineering traditionally involves empiricism and lacks a solid fundamental underpinning based on the controlling mechanisms. These design shortcomings exist due to deficiencies in the fundamental understanding of geotechnical interface behaviors and the lack of test methods and devices available to directly measure interface properties in situ. The current work strives to improve the state of geotechnical knowledge and design with regard to interface behavior through fundamental laboratory studies and the development and use of a new in situ testing device. The current investigations are focused across a range of scales from micromechanical interactions to full scale field implementation. A series of laboratory investigations at the micromechanical level have been performed, specifically aimed at investigating the mechanisms controlling granular interactions against conventional and textured friction sleeves, and hook and loop type interactions present within textured geomembrane - geotextile systems. Additionally, a new in situ testing device has been designed and developed, the Multi Piezo Friction Attachment (MPFA), to allow for the characterization of geotechnical interface properties in situ within the context of an effective stress framework. The MPFA simultaneously provides four independent measures of interface friction (f

A unique approach for lightweight multifunctional composites was developed using Fe3O4 nanoparticles and polypyrrole-coated Fe3O4 particles as fillers. Fe3O4 particles are a good candidate for filler in a multifunctional composite system because they can reinforce mechanical properties of a polymer matrix and impart magnetic properties into a composite. Polypyrrole coating on Fe3O4 particles was utilized to incorporate electrical conductivity to the properties of composites. The effects of filler size and filler content were studied on both the mechanical and electromagnetic properties. Fe3O4 nanoparticles improved fracture toughness, but they compromised strength and modulus. Polypyrrole-coated Fe3O4 has potential for multifunctional material applications because the coating allows for concurrent increase in magnetic permeability and electrical conductivity in a composite. The polypyrrole coating also improved the strength of the composite. Fe3O4 nanoparticles were a major part of this work from their synthesis to their application in composites. The surface effect on magnetic properties was analyzed for Fe3O4 nanoparticles, resulting in a more accurate calculation of the magnetically dead layer thickness than previously reported. The results from this work contributed to further understanding of synthesis and characterization of magnetic nanoparticles, fabrication and characterization of nanocomposites, and design and development of lightweight multifunctional materials. Although the properties of the fabricated composites require further improvement, the methodology and approach provide a basis for future work in development of lightweight multifunctional composites.