This thesis describes the development and the use of quantitative deuterium Nuclear Magnetic Resonance spectroscopy (NMR) as a tool in two areas of environmental research: the study of long term climate-plant interactions and the source tracking of persistent organic pollutant. Long-term interactions between plants and climate will influence climate change during this century and beyond, but cannot be studied in manipulative experiments. We propose that long tree rings series can serve as records for tracking such interactions during past centuries. The abundance of the stable hydrogen isotope deuterium (D) is influenced by physical and biochemical isotope fractionations. Because the overlapping effects of these fractionations are not understood, studies of the D abundance of tree rings led to conflicting results. We hypothesized that both types of fractionations can be separated if the D abundance of individual C-H groups of metabolites can be measured, that is if individual D isotopomers are quantified. The first paper describes a technique for quantification of D isotopomers in tree-ring cellulose by NMR. The technique showed that the D isotopomers distribution (DID) was non-random. Therefore, the abundance of each isotopomer potentially contains individual information which suggests an explanation for the conflicting results obtained by measuring the overall D abundance (dD). In the second paper, this technique was used to study hydrogen isotope exchange during cellulose synthesis in tree rings. This revealed that some C-H positions exchange strongly with xylem water, while others do not. This means that the exchanging C-H positions should acquire the D abundance of source water, which is determined by physical fractionations, while non-exchanging C-H positions of tree-ring cellulose should retain biochemical fractionations from the leaf level. Therefore, the abundance of the corresponding D isotopomers should contain information about climate and physiology. When analysing tree-ring series, the DIDs should reflect information about temperature, transpiration and regulation of photosynthesis. In the third paper, we showed that CO2 concentration during photosynthesis determines a specific abundance ratio of D isotopomers. This dependence was found in metabolites of annual plants, and in tree-ring cellulose. This result shows that D isotopomers of tree-ring series may be used to detect long-term CO2 fertilisation effects. This information is essential to forecast adaptations of plants to increasing CO2 concentrations on time scales of centuries. In the fourth paper, the source of persistent organic pollutants in the environment was tracked using DID measurements. The dD values of two compounds of related structures were not enough to show indisputably that they did not originate from the same source. However, the DIDs of the common part between the two compounds proved that they did not originate from the same source. These results underline the superior discriminatory power of DIDs, compared to dD measurements. The versatility of DID measurements makes them a precious tool in addressing questions that can not be answered by dD measurements. / Betson, Tatiana R

Background and objective: Major risk factors for congestive heart failure (CHF) are myocardial infarction, hypertension, diabetes, atrial fibrillation, smoking, left ventricular hypertrophy (LVH) and obesity. However, since these risk factors only explain part of the risk of CHF, we investigated whether persistent organic pollutants (POPs) might also play a role. Methods: In the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) study, left ventricular ejection fraction, (EF), E/A-ratio and isovolumic relaxation time (IVRT), were determined by echocardiography and serum samples of 21 POPs were analyzed in serum measured by high-resolution chromatography coupled to high-resolution mass spectrometry (HRGC/HRMS) in 998 subjects all aged 70 years. Results: In this cross-sectional analysis, high levels of several of the polychlorinated biphenyls (PCB congeners 99, 118, 105, 138, 153, and 180) and octachlorodibenzo-p-dioxin (OCDD) were significantly related to a decreased EF. Some POPs were also related to a decreased E/A-ratio (PCBs 206 and 209). All the results were adjusted for gender, hypertension, diabetes, smoking, LVH and BMI, and subjects with myocardial infarction or atrial fibrillation were excluded from the analysis. Conclusions: Circulating levels of POPs were related to impairments in both left ventricular systolic and diastolic function independently of major congestive heart failure risk factors, suggesting a possible role of POPs in heart failure.

Sewer trenches usually contain material with a higher hydraulic conductivity then the adjacent soil. Thus they can serve as paths of preferential flow in a polluted area. Wastewater from factories can also leak from wastewater pipes and pollute the soil in the sewer trenches. The purpose of this project was to investigate pollutions in sewer trenches and in sewer pipes in the industrial area of Köpmanholmen, 20 km south of Örnsköldsvik in the north of Sweden. To make an estimation concerning the potential of transport of pollutions in sewer trenches, hydrological calculations were performed. Leakage to any greater extent did not seem to be a problem in the area. This is the case both for the concrete and the wooden pipes that have served as factory wastewater pipes. A large transport in the lengthwise direction of the sewer trenches was not shown to exist. Instead the greatest risk of transport from a polluted area seems to come from infiltration into wastewater pipes, where the pollutants can flow readily to the recipient or wastewater treatment plant. / Rörgravar innehåller ofta grövre material med högre hydraulisk konduktivitet än omgivande jord och kan därför tjäna som spridningsvägar från förorenade områden. Avloppsvatten från fabriksområden kan också misstänkas ge upphov till föroreningar i rörgravar via läckage från avloppsrören. Detta arbete har haft som mål att utreda föroreningssituationen i ledningsgravar och avloppsledningar på Köpmanholmens industriområde, ca 2 mil söder om Örnsköldsvik. För att bedöma ledningsgravarnas potential att sprida föroreningar har också hydrologiska beräkningar har gjorts. Läckage i någon större omfattning från avloppsledningar har inte kunnat påvisas. Detta gäller både betongledningar och den trätub som har utgjort fabriksavlopp på området. Inte heller har någon föroreningsspridning kunnat påvisas i ledningsgravarnas längdriktning. Den största risken för spridning av föroreningar verkar istället vara via infiltration till avloppsledningarna. Detta ger en snabb transport från förorenade områden till recipient eller reningsverk.

The management of stormwater runoff is a particular challenge for communities in karst regions. Most guidelines for compliance with regulations for stormwater monitoring and mapping pertain to non-karst environments. It can be argued that effective stormwater management is even more essential to karst regions because stormwater receives little or no natural filtration as it is transferred through conduits in the subsurface and the buildup of pollutants underneath can be detrimental to community and environmental health if not effectively mitigated. Because of the limited resources available to determine how stormwater runoff carries potential pollutants across the surface before being transferred to the karst subsurface and then reentering back on the surface across the landscape, this study aims to use geographic information systems (GIS) to investigate this problem. The objectives of this study are twofold. The first objective is to understand the transport mechanisms for stormwater runoff and how the movement through karst systems differs from non-karst systems, especially in regards to the surface and subsurface interactions. The second objective is to develop a general procedure for predicting stormwater runoff pathways in karst regions using GIS technologies and spatial analysis techniques – including identifying which data and techniques are essential to analyze surface and subsurface processes - to improve stormwater monitoring effectiveness. The premise of this study is broken down into a conceptual model with three significant components: Surface Input (stormwater runoff on surface), Subsurface Transport (stormwater transport through subsurface), and Output to Surface (output of stormwater to the surface via springs). The first component utilizes Hydrological Analysis and Network Analysis techniques to determine stormwater runoff pathways from potential point-source pollutant sites across surface to injection points where runoff enters subsurface. The second component uses Spatial Interpolation Techniques and Hydrological Analysis to predict subsurface accumulation areas that collect runoff from injection points and subsurface conduit pathways to output locations. The third and final component examines the output of the runoff back to the surface and identifies the locations where stormwater runoff can be sampled. The analyses of the Surface Input component proved to be effective in predicting the behavior of stormwater runoff between pollutant sites and their corresponding injection points. The analyses of the Subsurface Transport captured the overall patterns in the inferred dye tracing pathways that were used as the control dataset. The Output to Surface established the linkages among RCRA sites, their corresponding injection points and ultimately their output springs. These findings are very useful in developing informed stormwater sampling strategies and plans. In future investigations, these results could be verified with stormwater sampling and additional dye tracings and can be improved in two ways: more complete datasets of all stormwater features in the area – especially springs and drywells, and a more extensive and equally distributed dataset for groundwater depths across the study area to create a more accurate interpolated potentiometric surface.

Naturally occurring plant derived phenols can be degraded through bacteria in swine waste. Chlorinated phenols, which are not naturally present in the environment, are toxic and generated from industrial activities as such petrochemical, pharmaceutical, plastic, rubber, pesticide, iron, steel, paper production, coal conversion, wood preserving, and cellulose bleaching. Large scale coal gasification and carbonization plants are another source of chlorinated phenols. Although not normally present in the environment, chlorinated phenols are structurally similar to many plant derived phenolics. It is our hypothesis that bacteria located in swine wastes may also have the ability to degrade chlorinated phenols. Identifying situations (and organisms) in which degradation of pollutants occurs is important field of research. Experimental work was focused on measuring the degradation of seven chlorinated phenols in swine waste using solid-phase micro-extraction (SPME) and gas chromatography(GC). Microbes in the waste perform respiration or fermentation to obtain the energy they need to carry out their life processes. Fermentation is a process in which electrons are transferred from one organic substrate to another and which results in incomplete degradation of organic compounds. Anaerobic respiration is a process in which organic substrates are degraded completely to CO2, but using substances other than oxygen as the terminal electron acceptor (such as Fe(III), NO3- or SO42-). Anaerobic respiration using these alternative electron acceptors provides an easier pathway for degradation of aromatics than fermentation alone. Usually the abundance of these electron acceptors in waste is low since microbes consume them readily and thus they must be added to the mixture. Our work focused on development of methods for the quantification of chlorinated phenols in swine wastes and results of bioremediation research. In this study, chlorophenols were extracted by SPME and analysed by GC. This research project mainly focused on the anaerobic degradation of chlorophenols in swine waste. It was observed that the decreased concentration of the chlorophenols was likely due to partitioning of the chlorophenols to solids, sticking to glass bottles and by bacteria present in the swine waste. In summary, it was observed that by ANOVA and gas production analysis 2,6-dichlorophenol and 2,4,5-trichlorophenol were likely to be degraded by bacteria present in swine waste.

This work is study 71 kinds of volatile organic compounds (VOCs) in the sewer system of a metropolitan city during dry/wet weather. The VOCs contains alkanes, alkenes and alkynes, aromatics, chlorinated organics, sulfides, ketones and ethers. The purpose of this work estimated the emission rates of VOCs and cancer risk within 12 kinds of hazardous air pollutants (HAPs) will be part of the investigation 26 HAPs by using risk assessment. TVOCs (concentrations of total VOCs) in dry weather was higher than that in wet weather for both sewer systems. The concentration distributions of dominant were KB7 (C3) in the A (B) sewer system. This system collected sewage from harbor and industrial park. During dry and wet weather, the most common VOCs were chlorinated organics and alkanes in the A sewer system, respectively. The main contribution were chloroethene and isopentane; the most common VOCs were aromatics in the B sewer system. The main contribution was m / p-Xylene. This results show that the most emission rates of TVOCs is C3 (13,834.79 mg/hr) during dry weather and KB2 (1875.25 mg/hr) during wet weather. The emission rates of K1

This study measured Ambient concentrations of air pollutants and Volatile Organic Compounds (VOCs) in industrial park in Kaohsiung City. The spatial distribution was investigated during different time periods and seasons. The ozone formation potential (OFP) of VOCs species were evaluated based on the maximum incremental reactivity (MIR). Also, this study using factor analysis to estimate the polluted source. The season distribution of air pollutants showed concentration in spring higher than summer, owing to air activities of summer are acute include wet precipitation, photochemical reaction, and convection. The time period distribution showed the results which NOx and O3 concentration occurred peaks at 7:00 − 8:00, 18:00 − 19:00 and 13:00 − 16:00, respectively. The reason is photochemical reaction, lead to concentration trend with time of NOx inversely to O3. The concentration trend with time of CO and PM10 similar to NOx. The polluted sources were estimated mobile. By the way, O3 is proportional to temperature, but it is Inversely proportional to humility. The seasons distribution of VOCs showed most abundant species included 2-butanone, toluene, and n-pentane in spring, while included toluene, acetone, m,p-xylene, and methyl methacrylate in summer. According to percent composition, most abundant categories in spring and summer were both aromatics, ketones, and alkanes. The TVOC concentration was spring (164.6 £gg/m3) higher than summer (116.4 £gg/m3). The time periods distribution of VOCs showed most abundant categories included aromatics and ketones in morning and evening, while included aromatics and alkanes in night. The TVOC concentration of evening (163.2 ¡Ó 62.7 £gg/m3) was highest, followed by night (159.9 ¡Ó 87.4 £gg/m3), Lowest was morning (98.4 ¡Ó 32.3 £gg/m3). Results showed alkanes and alkenes own higher concentration in night, ketones and esters in evening, and aromatics in evening and night. The reason is related with sunshine, inversion layer, and lower wind speed. By the way, TVOC is proportional to temperature. In spring, the OFP was 566.0 £gg-O3/m3, OFP/TVOC was 3.44. In summer the OFP was 629.3 £gg-O3/m3, OFP/TVOC was 5.41. It was worth mentioning highest OFP categories in spring and summer was both aromatics (332.2 £gg-O3/m3, 380.3 £gg-O3/m3), and highest OFP species was toluene (138.8 £gg-O3/m3) and methyl methacrylate (171.7 £gg-O3/m3) , respectively. The results from factor analyses showed the predominant source included mobile polluted source, petrol evaporation, related electronic industry, metallurgy industry, refinery, and architectural coatings escape in spring. The predominant source included mobile polluted source, petrol evaporation, plastic industry, steel industry, and related electronic industry in summer.

ABSTRACT Three-dimensional modeling on the aerodynamics of airflow and diffusion of air pollutants in a longitudinal-ventilated traffic tunnel was carried out. The model takes ventilation fans, traffic flow rate, speed, emission factor and piston effect of moving vehicles into consideration. Turbulent flow and dispersion of gaseous pollutants in road tunnels were solved numerically using the finite volume method. Traffic emissions were accordingly modeled as banded line sources along the tunnel floor. The effects of fan ventilation, roughness and piston effect of moving vehicles on the air flow and pollutant dilution are examined. Concentrations of gaseous pollutants CO, NOX, SO2 and THC (total hydrocarbons) at three axial locations in the tunnel, together with traffic flow rate, traffic speed and types of vehicle were measured. Case study was conducted on the Cross-Harbor Tunnel and the Chungcheng Tunnel in which on-site measurements of traffic flow were also conducted concurrently to provide traffic emission data to the tunnel environment for numerical simulation and comparisons. The aim of this study was to understand the spatial variation of air pollutants generated by traffic emissions and evaluation of ventilation performance and piston effect of moving vehicles on dilution of air pollutants in these tunnels. The results show that the major emission sources of CO are passenger cars and motorcycles, while major emission sources of NOx are trucks. Pollutants convect downstream with the wind generated either by longitudinal ventilation fans and/or moving vehicles, thus causing increasing pollutants concentrations with increasing downstream distance. The piston effect of moving vehicle alone can provide 64% ~ 85% increase of wind speed in Chungchen Tunnel and 13% ~ 20% in Cross-Harbor Tunnel. When all fans are on, showing 185% ~ 328% and 120% ~ 182% increases in Chungchen Tunnel and Cross-Harbor Tunnel, respectively. The piston effect of moving vehicle alone can provide 14% ~ 32% dilution of air pollutants in the Chungcheng Tunnel. The piston effect of moving vehicles is compounded with ventilation fans, showing a 47% ~ 66% dilution effect when all fans are on. For the Cross-Harbor Tunnel, the piston effect of moving vehicle alone can provide 9% ~ 23% dilution of air pollutants and 36% ~ 74% dilution effect when all fans are on. The results reveal that cross-sectional concentrations are non-uniformly distributed and that concentrations rise with downstream distance. When all fans were turned off, wind speed in tunnels would be considered as constant, and gaseous pollutants concentration agree with linearly alone the tunnel.

Air quality was influenced by many factors, in South Taiwan, air pollutants transportation caused by monsoon or sea-land breeze that may caused high air pollution events. Air pollutant generated by human activity on daytime, then transported and accumulated at sea region by land breeze during the nighttime. Unfortunately, air pollutants that accumulated over sea on night may transport back to land by sea breeze on daytime. Besides, monsoon may carry air pollutants from other regions to South Taiwan and caused high air quality event. Till now, air quality influenced by sea-land breeze and monsoon were not verified in South Taiwan. This study investigated the temporal variation and spatial distribution of air pollutants in the atmosphere around the coastal region of South Taiwan. Ambient air pollutants were simultaneously monitored both inland and offshore. Inland monitoring was conducted at two sites associated with fourteen national air quality monitoring stations, while offshore monitoring was conducted at two sites both in an island and on the boat. A protocol of ambient air quality monitoring was conducted for forty-eight hours. Gaseous air pollutants (i.e. CO, SO2, NOX, THC, and O3) were continuously monitored instrumentally. Data obtained from both inland and offshore monitoring were applied to plot the concentration contour by a software SURFER. Hourly variation of air pollutant concentrations was further used to study the influences of sea-land breezes on the transportation of air pollutants around the coastal region of South Taiwan for different seasons. In August and November, 2006 and May, 2007, sea-land breeze was observed during sampling period and sea breeze arise from 9:00 A.M. to 24:00 P.M. The average wind velocity was 1~4 m/s during the sampling period. In January and March, 2007, prevail wind direction was north direction and northeast direction (270o~30o), that was influenced by northeast monsoon during the sampling period. The average wind velocity was 2~4 m/s. The results showed that distribution of air pollutants, including O3, NOX, THC, and CO influenced by sea-land breezes, particularly for ozone. Air pollutants transported to sea region during the nighttime, and transported back at daytime. This phenomenon cause air pollutants accumulated between Kao-Ping and sea region. In general, NOX generated by transportation and industrial process, thus high concentration of NOX appeared during traffic congestion period and at industry region, mainly Kaohsiung city and Linyuang industrial region. However, sea-land breeze effect upon transportation of air pollutants wasn¡¦t obvious for SO2. High SO2 concentration appeared at Linyuang industrial region and Siaogang at daytime, and transported to region along the coast. During northeastern monsoon season, northeast winds obstructed by Central Mountain Range cause air pollutants accumulated at Kao-Ping region. High NOX concentration appeared at Kaohsiung City and Linyuang industrial region. SO2 accumulated at Siaogang and Linyuang during the nighttime might be caused by high atmospheric pressure system and blew air pollutants to Linbian. CO was accumulated at Siaogang at daytime and transported to Donggang, while THC was accumulated at Donggang whole day.

Evolution of strategies for biodegradation of synthetic organic pollutants relies on recruitment of genes from catabolic pathways for natural compounds. Investigation of metabolic diversity in nature can provide insight into biochemical strategies that could be recruited for bioremediation of pollutants. As part of a search for novel metabolic diversity we isolated soil bacteria able to degrade 2-nitroimidazole (2NI) and 5-nitroanthranilic acid (5NAA), and determined the biochemistry and molecular biology of their biodegradation pathways. 2NI and its analogs are increasingly used as prodrugs for the treatment of both tuberculosis and cancer. The biodegradation of 2NI by a soil Mycobacterium sp. is initiated by an unusual hydrolytic denitration. The reaction is catalyzed by a novel nitrohydrolase with a divergent sequence and represents the discovery of a previously unreported drug resistance mechanism in soil prior to its identification in clinical situations. 5NAA is the starting material for various nitroaromatic compounds and dyes. The biodegradation pathway of 5NAA is initiated by an unusual hydrolytic deamination. The corresponding gene is very distantly related to biochemically characterized genes in the NCBI database. The nitro group of 5NAA is eliminated as nitrite during the spontaneous formation of lactones from a ring fission product, a previously unreported mechanism. Degradation pathways of 5NAA and 2NI serve as precedents for those of nitroaniline and nitroimidazole pollutants. The work supports the hypothesis that the study of the metabolism of natural organic compounds selected on the basis of unusual structural features and ecological roles can reveal new metabolic diversity.