An extensive use of chemicals in countless consumer products has resulted in human exposure to several persistent organic pollutants (POPs). Sufficient knowledge about their chemical composition properties and environmental faith is required, to be able to proper risk assess and regulate the substances. Significant data gaps exist regarding knowledge of actual exposure to humans and toxicological effect data. The objective of this thesis was to add human exposure data of a few POPs from four case studies. The analytes discussed in this thesis are polychlorinated dibenzo-p-dioxins and furans (PCDDs/PCDFs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD). Three European populations were studied. Milk was analysed from a group of women, who were accidentally exposed to high levels of 2,3,7,8-TetraCDD (TCDD) in Seveso, 1976. Still today, twice as high TCDD levels were recorded in the milk, compared to background concentrations. Serum was analysed from mothers and their infants from The Netherlands. Cord serum contained equal amounts of POPs as in mother’s blood, indicating non-hindered placenta transfer. Serum analysed from Swedish men and women with a high fish intake had elevated PCB and PCB metabolite (OH-PCB) levels. Additionally, butter was collected worldwide and shown to be a suitable matrix for dairy product survey of POPs. The exposure levels in the four papers were compared to recently reported exposure levels in Europe. It is indicated in the thesis that the PCDDs/PCDFs and PCBs toxic equivalency (TEQ) levels are of concern, i.e. the ratio between threshold levels for adverse health effects and TEQ exposure levels is lower than requested margin of safety. Average levels of PBDE/HBCDD in the European population are estimated to be of no concern today, but for individuals with intakes at the 95th percentile are the current margins of safety small.

The remote sub-Arctic/Arctic environment has due to human activities become a sink for organohalogen contaminants (OHCs). These OHC include traditional contaminants such as polychlorinated biphenyls (PCBs), DDTs and technical mixtures of polybrominated diphenyl ethers (PBDEs), all included in the Stockholm Convention list of persistent organic pollutants (POPs). Other OHCs, currently under evaluation to be included among the POPs i.e. short chain chlorinated paraffins (SCCPs) and hexabromocyclododecane (HBCDD) are also found in these environments as well as a whole range of other OHCs. The main objective of this thesis is to increase the knowledge about the presence of OHCs in a high trophic Arctic shark species, the Greenland shark (Somniosus microcephalus). The Greenland shark is an opportunistic feeder, occasionally feeding at the top of the Arctic marine food chain. Furthermore may this species have a life span in excess of 100 years and is probably among the oldest of any fish species. These traits make the shark prone to accumulate elevated concentrations of OHCs. This has shown to be true for the Greenland sharks studied and most of the targeted OHCs were determined in the species. The highest concentrations were observed for the DDTs, ranging up to 26 μg/g fat. Other OHCs reported that are of special interest are SCCPs and brominated flame retardants used as replacement products to PBDEs; pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Also a range of OHCs whose origin is assumed to be natural, were shown to be present in Greenland sharks. This thesis is stressing the fact that even though the use of certain OHCs has been banned for decades they are still present at high concentrations in the deep waters of the Arctic. Therefore it is of major importance to continue to monitor the fate of traditional and emerging OHCs in the environment, and for this purpose the Greenland shark is an excellent species. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

Dargestellt werden die Verursacher von Luftschadstoffen und Treibhausgasen, u. a. Groß- und Kleinfeuerungsanlagen, Verkehr und Landwirtschaft sowie der prozentuale Anteil ihrer Emissionen. Dazu gehören beispielsweise Kohlendioxid, Methan, Lachgas und die Luftschadstoffe Kohlenmonoxid, Schwefel- und Stickoxide, leicht flüchtige Stoffe, Staub und Feinstaub, Ammoniak, persistente organische Stoffe und Schwermetalle. Nach den deutlichen Verbesserungen der Luftqualität in den 1990er-Jahren haben sich die Emissionen von Luftschadstoffen und Treibhausgasen in den letzten 10 Jahren auf einem stabilen Niveau eingependelt. Mit Ausnahme von Kohlendioxid und Schwefeldioxid liegt Sachsen bei den Luftschadstoffen unter dem Bundesdurchschnitt.

Synthesis of heat shock proteins (Hsps) in response to elevated temperatures and other denaturing agents (including UV, heavy metals, and energy depletion) is a common productive response of prokaryotic and eukaryotic cells. Therefore, increasing in production of heat shock protein has been considered a sign of cells under stress. The phylum Sipuncula comprises of about 300 species worldwide; they are bilaterally symmetrical, unsegmented, and deposit feeding marine worms common in the substrate of wetland. In this research, I studied the dominant species Sipunculus nudus and analyzed it proteomics to reveal how it responses to persistent organic pollution. In order to compare the difference between HSP70 and HSP90, Sipunculans were sampling from two wetland (Xiangshan and Wanggong) in Hsinchu and Changhua,, respectively. The results showed that the concentrations of PAHs and OCPs both in substrate and S. nudus tissues from Xiangshan were higher than Wanggong. The concentrations of PAHs and OCPs in both areas showed that the environmental- sediment levels were higher than the sediment inside the gut or the body tissues. Principal component analysis showed that the compositions in S. nudus from both area were similar; however PAHs compositions from the environmental sediment or the sediment of the gut were similar. When the concentrations of HSP70 and HSP90 between both areas were compared, HSP70 expressions did not significant differed in both areas, while HSP90 express was higher in the S. nudus from Xiangshan than Wanggong. For S. nudus Hsp90 was upregulated in highly polluted area (i.e. Xiangshan). I propose that tissue expression of HSP90 plays an important role in the survival of S. nudus, and detection of HSP90 may provide pollution information of the surrounding environment.

Polybrominated diphenyl ethers (PBDEs) are anthropogenic chemicals whose environmental behavior is similar to the well-known polychlorinated biphenyls (PCBs). Few studies have quantified the amount and distribution of PBDEs in the southern hemisphere and Antarctica. The analyses reported in this dissertation document the levels of PBDEs in lichens, mosses and seabird eggs collected at King George Island, Antarctic Peninsula. The analyses were carried out using Gas Chromatography/Electron Impact-Mass Spectrometry (GC/EI-MS). Employing the ion stacking technique lowered detection limits and ensured instrument selectivity and sensitivity to the compounds of interest. Lichens and mosses absorb PBDEs directly from the atmosphere and their contamination indicates that long-range transport is the primary source of these chemicals to King George Island. The congener patterns of PBDEs in plants indicate that commercial mixtures of Penta-BDE and Octa-BDE have reached Antarctica. Differences in the levels of PBDEs observed in lichens and mosses are probably due to factors that govern the uptake of PBDEs from the atmosphere. Contamination in lichens showed a positive correlation with local precipitation. Conversely, absorption of PBDEs in mosses appears to be controlled by other plant-specific factors. Marine phytoplankton-derived aerosols are hypothesized to play an important role in the atmospheric transport of PBDEs to the Antarctic environment. PBDEs in south polar skua eggs revealed much higher concentration than in penguin eggs. This is likely associated with the northward migration of these seabirds during the non-breeding season. While penguins reside year-round in Antarctica, south polar skuas migrate northward and can be seen in boreal oceans during the austral winter. Distribution of PBDEs in penguin eggs matches the pattern found in local vegetation suggesting a common source for the chemicals. In contrast, the congener pattern of south polar skuas suggests that birds breeding at King George Island are wintering in the northwestern Pacific Ocean. A potential metabolism of PBDEs in penguin eggs during the incubation period seems to be limited. Most congeners were unaltered from source material in the eggs of chinstrap and gentoo penguins. Low levels of PBDEs, short incubation periods and energy constraints may explain these observations.

The Kaoping River basin is the largest and the most intensively used river basin in Taiwan. It is 171-km long, drains a catchment of more than 3,250 km2. Based on the current water quality analysis, the Kaoping River is heavily polluted. Concern about the deteriorating condition of the river led the Government of Taiwan to amend the relevance legislations and strengthen the enforcement of the discharge regulations to effectively manage the river and control the pollution. Investigation results demonstrate that both point and non-point source pollutants are now the causes of biochemical oxygen demand (BOD), nutrients, and pathogens in the river. The main water pollution sources are livestock wastewater from hog farms, municipal wastewater, industrial wastewater, non-point source (NPS) pollutants from agricultural areas, and leachate from riverbank landfills. The current daily BOD, NH3-N, and TP loadings to Kaoping River are 74,700, 39,400, and 5,100 kg, respectively. However, the calculated BOD, NH3-N, and TP carrying capacities are 27,700, 4,200, and 600 kg per day. To protect public health and improve the river water quality, the comprehensive management and construction strategy is proposed. The proposed strategy includes the following measures to meet the calculated river carrying capacity: (1) hog ban in the entire Kaoping River basin, (2) sewer system construction to achieve 30% of connection in the basin within 10 years, (3) removal of 10 riverbank landfills, and (4) enforcement of the industrial wastewater discharge standards. After the implementation of the proposed measures, the water quality should be significantly improved and the BOD and nutrient loadings can be reduced to below the calculated carrying capacities.

The Hsuehshan tunnel, whose length is about 12.9 kilometers, is the longest tunnel in Taiwan and Southeast Asia. Since the tunnel is used, it reduces the traveling time from Taipei to Ilan and brings the convenience of transportation; but the vehicles and pollution sources are added. Furthermore, the concentrations of pollutants are increased by accumulation in the long tunnel. This study estimates the effects of automobile tailpipe emissions in the Hsuehshan tunnel on the air quality of neighboring areas by using Atmospheric Dispersion Modelling System for Roads (ADMS-Roads). This work simulates carbon monoxide (CO), nitrous oxides (NOx) and sulfur dioxide (SO2) at two sites (Pin-Ling and Tou-Cheng management centers) in northern Taiwan in winter of 2008. The average concentrations of CO, NOx and SO2 at Pin-Ling (Tou-Cheng) management centers respectively are 0.49 (0.55) ppm, 10.60 (14.83) ppb and 4.80 (7.47) ppb on non-holiday and 0.66 (0.64) ppm, 16.88 (15.12) ppb and 4.70 (4.20) ppb on holiday. It shows that the concentrations of pollutants on holiday are higher than on non-holiday by increasing vehicles. Simulated results show that effects of traffic exhaust in the tunnel on the air quality of neighboring areas are less. Estimations using the ADMS-Roads suggest that the emissions are not the predominant contributors at two sites. The effect is the highest with northern (northeastern) winds at the southern (northern) area of the Hsuehshan tunnel. Comparisons between simulations and measurements at both sites are satisfactory. Simulated values are generally in agreement with measured values, with a correlation coefficient of R = 0.37 ¡V 0.81, the index of agreement (IOA) = 0.58 ¡V 0.77, and the normalized mean square error (NMSE) = 0.03 ¡V 0.25. The ADMS-Roads will be applied to assess the environmental impact while the tunnel will be allowed more types of vehicles to drive in the future.

This research investigate and analysis 77 kinds of volatile organic compounds (VOCs) in the sewage system of a southern urban area (A, B, C, D, E and F). The 77 kinds of VOCs will be divided into BTEX, chlorine-containing hydrocarbons and non-chlorine-containing hydrocarbons, and to estimate the emission of 27 kinds of hazardous air pollutants (HAPs). Cancer risk within 12 kinds of HAPs will also be part of the investigation by using Risk Assessment. In terms of consistency, except A1, D5 and E, VOCs are required mainly of non-chlorine-containing hydrocarbons at other areas, and main contribution species are ethylene, acetylene and ethane. There are 55.05 % of BTEX (1298.2 £gg/m3) and 35.51 % of non-chlorine-containing hydrocarbons (837.6 £gg/m3) in A1, but the main contribution are toluene, m-xylene and p-xylene. In D5, there is 76.39 % of BTEX (3744.7 £gg/m3) and the main contribution are m-xylene, p-xylene and toluene. In E, there is 80.02 % of chlorine-containing hydrocarbons (4807.1 £gg/m3) and the main contribution are chloromethane and toluene. Results show that the most emissions of total HAPs is D5 (12195.3 mg/hr), followed by B2 (4602.9 mg/hr), E (2659.4 mg/hr), A4 (2043.7 mg/hr) and A1 (1526.2 mg/hr). BTEX represent the largest proportion of the emissions of total HAPs in D5, A4 and A1. Chloroethene represents the largest proportion of the emissions of total HAPs in B2, followed by trichloroethene and tetrachloroethene. Chloromethane represents the largest proportion of the emissions of total HAPs in E. The most cumulative cancer risk in the sewage space is B2, followed by C2 and A3. The main contribution of the average cancer risk (not include B2) in a southern urban area are 1,1,2-trichloroethane, 1,2-dichloroethane and 1,4-dichlorobenzene.

Microcosm studies were conducted beginning with three xylene isomers: ortho-xylene, meta-xylene and para-xylene; and continued with the four mononitroxylene (MNX) isomers, culminating with testing ten dinitroxylene (DNX) isomers. Soil samples were obtained from a historically contaminated site with high levels of dinitrotoluene (DNT), trinitrotoluene (TNT) and dinitroxylene (DNX) and used as the inoculum for microcosm tests. The microcosm method of different isomers was based on the previous work on biodegradation of nitrotoluene. As it was demonstrated previously that 2,4-DNT degrading bacteria were present at the site, it was hypothesized that these may be capable of transforming or cometabolizing some of DNX isomers. Thus, DNX cometabolism studies were conducted in the presence of 2,4-DNT degrading bacteria. The presence of xylene and 2,4-DNT degrading was confirmed in this thesis. Meanwhile, several MNX and DNX isomers showed degradability in microcosm studies. Cometabolism studies showed that four DNX isomers could be cometabolized by 2,4-DNT enrichment.

Thesis (Ph. D.) in Ecology and Environmental Science--University of Maine, 2003. / Includes vita. Includes bibliographical references (leaves 137-163).