採用主動式XAD-2樹脂吸附及被動式半滲透膜採樣裝置(Semipermeable membrane device, SPMD) 搭配確效參考化合物(Performance reference compounds, PRCs)，測量河口水中生物可利用性多環芳香烴(Polycyclic aromatic hydrocarbons, PAHs)濃度。由XAD-2樹脂分析結果(Cw)顯示，表水和底水之總PAHs濃度分別為6.63和9.58 ng L−1；採用5個PRCs進行三次多項式權重回歸，取得最適之現地採樣速率（Sampling rate, Rs, L d−1），進而估算河口水中之生物可利用性PAHs濃度 (CSPMD)：表水5.87 ng L−1及底水9.15 ng L−1；表水為湍流使其Rs值較高，底水較少湍流，Rs值主要以擴散為主，於高分子量PHAs呈下降趨勢。將CSPMD與Cw進行比較，二者在濃度分佈、環境指紋特徵來源及毒性當量結果相近；表水之PAHs為石油來源，而底水PAHs為燃燒性來源。
被動式半滲透膜裝置（SPMD）之現地採樣速率（Rs）與流率及溫度之關係進行研究，採用PRCs進行三次多項式權重回歸，取得現地之最適Rs值，進而估算海水中之生物可利用性PAHs濃度，並建置研究區域內的SPMDs設備經驗公式。Rs值未隨現地環境條件不同而有所改變(流速範圍5.3至40.5 cm sec–1及溫度範圍9.8至25.2°C)，其結果與文獻上實驗室研究結果相異，該差異主要源自SPMD裝置之網籠效應，及各研究之流率和溫度範圍不同所致。使用現地條件下建置的經驗公式，未來不需添加PRC即可計算Rs值，並可用於長期海洋環境監測。由SPMD於台灣海峽兩岸佈署之生物可利用性PAHs結果顯示，東岸濃度介於0.281至0.611 ng L–1；西岸濃度介於0.438至1.10 ng L–1；兩岸之生物可利用性PAHs來源及毒性差異，主要為兩岸能源使用不同所致。

Bioavailable polycyclic aromatic hydrocarbon (PAH) concentrations in the estuarine water of Kaohsiung Harbor were measured using XAD-2 resin and semipermeable membrane devices (SPMDs) calibrated with performance reference compounds (PRCs). The sum of the PAH concentrations from XAD-2 resin (Cw) in the surface and bottom water samples was 6.63 and 9.58 ng L–1, respectively. The variation in PAHs was higher in surface water. Cubic polynomial regressions using the sampling rate for five PRCs (Rs-PRC) provided estimated in situ sampling rates (Rs). The turbulent condition in the surface water was important in enhancing Rs; however, diffusion was relevant to the bottom water, which was less turbulent and showed decreasing Rs at high MW PAHs. The sum of the dissolved PAH concentrations estimated with the SPMDs (CSPMD) was 5.87 and 9.15 ng L–1 in the surface and bottom water samples, respectively. The surface and bottom water PAHs were derived from different sources.
The dependence of the in situ Rs of SPMDs passive sampler with the flow rate and temperature was also investigated. The in situ Rs values of SPMDs were obtained by using PRCs with weighted polynomial regression and were used to estimate the bioavailable PAH concentrations in the seawater. The empirical equation of the Rs value in the study area under the SPMDs equipment was established. The in situ Rs values were not found to vary with the flow rate (ranged 5.3 to 40.5 cm sec–1) and temperature (ranged 9.8 to 25.2°C). This field study is different from the literature reported laboratory study. The difference can be explained by cage effect and the different ranges of flow rate and temperature. This infers that PRCs could be exempted by using the established empirical equation under similar field conditions. Thus, use of SPMD empirical equations could benefit routine deployment in monitoring marine environment. Results of the SPMD deployment across the Taiwan Strait show that the sum of the bioavailable PAH concentrations ranged from 0.281 to 0.611 ng L–1 in the eastern side of Taiwan Strait and from 0.438 to 1.10 ng L–1 the western side. Distinct sources and toxicity of these bioavailable PAHs across the Taiwan Strait were observed and mainly resulted from different energy consumption.

審定書…………………………………………………………………… i
謝誌………………………………………………………………………ii
摘要…………………………………………………………………….. iv
Abstract…………………………………………………………………vi
Table of Contents……………………………………………………viii
List of Figures…………………………………………………………x
List of Tables………………………………………………………… xiii
Chapter 1 Review of the SPMD to estimate the bioavailable PAHs in
marine environment…………………………………………………….1
1.1. Bioavailable PAHs in marine environment…………………..1
1.2. Theory of SPMD……………………………………………….3
1.2.1. Models for SPMD-water exchange……………………………3
1.2.2. Rs sampling rate……………………………………………7
1.3. Objectives………………………………………………………9
Chapter 2 Measuring bioavailable PAHs in estuarine water using
semipermeable membrane devices with performance reference
compounds……………………………………………………………11
2.1. Introduction…………………………………………………11
2.2. Materials and methods………………………………………13
2.2.1. Chemicals………………………………………………. 13
2.2.2. Sampling…………………………………………………14
2.2.3. Analysis and sample processing……………………………16
2.2.4. Quantification and instrumental analysis……………………18
2.3. Results and discussion………………………………………20
2.3.1. Variation of PAHs in the water samples………………………20
2.3.2. PRC estimate of the field sampling rate constant……………..23
2.3.3. Comparison of PAH results from PRC-based SPMD and XAD-2..30
2.3.4. Principal component analysis and toxicity ……………………36
Chapter 3 The effects of flow rate and temperature on SPMD
measurements of the bioavailable PAHs in seawater………………41
3.1. Introduction…………………………………………………41
3.2. Materials and methods………………………………………43
3.2.1. Chemicals………………………………………………43
3.2.2. Sampling………………………………………………44
3.2.3. Analysis and sample processing……………………………46
3.2.4. Quantification and instrumental analysis…………………47
3.3. Result and discussion………………………………………49
3.3.1. PRCs estimated sampling rate………………………………49
3.3.2. Environmental parameters on sampling rate…………………53
3.3.3. Field empirical equation of the Rs value……………………57
3.3.4. The bioavailable PAH concentrations CSPMD…………………60
3.3.5. Principal component analysis………………………………63
Chapter 4 Conclusions and suggestions………………...…………67
4.1.Conclusions……………………………………………………67
4.2. Suggestions for future works………………………………69
References……………………………………………………………70
Appendix……………………………………………………………77
Curriculum vitae……………………………………………………….83

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