原油是由超過萬種的化合物組合而成，其中包含許多具生物毒性之化合物。經過煉製後的石油產品在工業革命後成為人類社會中不可或缺的物資，然而石油產品的使用的過程中具有洩漏的風險，為了釐清石油污染對於環境的影響，環境法醫技術可應用於油品洩漏事件之鑑識及監測，透過不同科學方法分析石油產品及其污染之特性，達成污染鑑識之目標，進一步提供責任歸屬與污染整治之相關資訊。
目前台灣公告以總石油碳氫化合物( Total Petroleum Hydrocarbon,TPH)作為主要油品洩漏之鑑定方式，台灣環保署以在2018年完成國內柴油化學指紋鑑定技術及鑑識流程，然而國內對於蒸餘燃料油與潤滑油之相關污染鑑識，尚未具有完整鑑定技術及鑑識流程，本研究以國內海上船隻常用之海運重柴油、MF-180海運燃油及陸上常用之LFO低硫鍋爐用油、2號燃料油以及CG4超優潤滑油作為研究樣本，利用氣相層析質譜儀(GC-MS)探討不同中重質餾分油品之化學指紋分布，主要分析化合物包含正烷類、Pristane、Phytane、多環芳香烴、烷基菲( Alkyl-Phenanthrene)、二苯并噻吩及烷基衍生物(Dibenzothiophene & Alkyl-Dibenzothiophene)、以及高沸點生物指標化合物(類萜烷、類固烷)等，透過定性定量分析，進一步建立診斷比值，提供重燃料油及潤滑油品之化學指紋鑑識資料。
從分析結果來看，石油煉製過程中之蒸餾過程，對於石油產品之化學指紋分布有著重要的影響，隨著蒸餾溫度就越高，油品中正烷類碳數、高環數多環芳香烴分布與多環芳香烴與二苯并噻吩之烷基化程度皆會增加，而重質燃料油與潤滑油中高沸點生物指標化合物類萜烷及類固烷為主要分布之化合物，在油品中的精製過程如脫硫製程與潤滑油煉製過程，皆會進一步影響油品之化學指紋，可根據油品製程對於油品化學指紋之影響，建立相關診斷機制。
根據不同化學指紋的分析結果，建立12種診斷比值可區別5種原生油品，其中有9種診斷比值可區分兩種燃料油與潤滑油品，本研究未來可進一步進行風化作用評估，建立國內蒸餘燃料油及潤滑油品受風化作用影響之化學指紋變化，或研究混合油品污染對化學指紋之影響，提升國內重燃料油與潤滑油之油品鑑識技術及污染整治之研究資料庫之全面性。

Crude oil is hugely mixture of ten thousands of individual hydrocarbons and nonhydrocarbons. Some of the compounds in crude oil have high toxicity to human and wildlife. The petroleum products are essential in modern society after the industrial revolution, but there has the risk of petroleum products spill during the using process which contains mining, transportation, refining, storage and using. For preventing the impact of the oil spill, the environmental forensic start to use on oil spill events identification and monitoring. The information from environmental forensic can help us to know oil spill events responsibility belonging and oil remediation monitoring.
In Taiwan EPA method, Total Petroleum Hydrocarbon(TPH) is the general method on the oil spill events identification. Taiwan EPA has established the survey methods and chemical fingerprint database of Taiwan’s diesel in 2018. However, for the heavy fuel and lubricant oil, we still have not enough study in Taiwan. This study focuses on Taiwan’s heavy fuel and lubricant oils chemical fingerprints. The samples contain diesel, heavy fuels and lubricant oils. We used Gas chromatography– mass spectrometry (GC-MS) to analyze eight different kinds of compounds in different petroleum products which contain N-alkane, Pristane, Phytane, 16 kinds of USEPA priority pollutants PAHs, Alkyl-Phenanthrene (Alkyl-PHA), Dibenzothiophene (DBT), Alkyl-Dibenzothiophene (Alkyl-DBT), Terpanes, Steranes. Through qualitative and quantitative analysis, this research tries to establish the diagnostic ratios which are based on the chemical fingerprinting of our target petroleum products.
From the result, the chemical fingerprinting is related to crude oil chemical fingerprint distribution. The fractionation processes and conversion processes are playing a more critical role in petroleum products. For example, the carbon range, alkylation of PAHs and DBT are increase as the distillation temperature increase. The high boiling points biomarkers (Terpanes and Steranes) are abundance in heavy fuel and lubricant oils. The hydrodesulfurization and dewaxing affect the chemical fingerprinting distribution of the petroleum products. Based on our result, we selected out 12 kinds of diagnostic ratios to distinguish five different petroleum products. Furthermore, we found out that 9 kinds of diagnostic ratios from these 12 kinds of diagnostic ratios can distinguish the heavy oil and lubricant oils. The further research can focus on oil weathering or mixing effects assessment to establish the full database of Taiwan heavy fuels and lubricant oils.

第一章 緒論　　　　　 1
1.1 研究動機　　　　　 1
1.2 研究目的　　　　　 2
1.3 研究架構與流程　　　　　 2
第二章 文獻回顧　　　　　 5
2.1 石油產品煉製與產品特性　　　　　 5
2.1.1 石油產品煉製程序　　　　　 5
2.1.2 石油產品特性　　　　　 6
2.2 石油產品化學指紋鑑定　　　　　 9
2.2.1 正烷類與無環異戊二烯　　　　　 13
2.2.2 生物指標化合物　　　　　 14
2.2.3 類萜烷　　　　　 15
2.2.4 類固烷　　　　　 18
2.2.5 16種多環芳香烴　　　　　 20
2.2.6 烷基多環芳香烴與雜環化合物(含硫基-多環芳香烴)　　　　　 22
2.3 石油化學指紋鑑定技術探討　　　　　 26
2.3.1 台灣現行油品污染調查　　　　　 26
2.3.2 CEN油品污染鑑識技術　　　　　 27
第三章 材料與方法　　　　　 31
3.1 實驗樣本　　　　　 31
3.2 實驗分析方法　　　　　 33
3.2.1 藥品及實驗器材事前準備　　　　　 33
3.2.2 萃取淨化實驗　　　　　 33
3.2.3 氣相層析質譜GC/MS 分析　　　　　 37
3.3 實驗品保與品管　　　　　 43
3.3.1 樣本保存　　　　　 43
3.3.2 實驗玻璃器皿清洗及藥品之選定　　　　　 43
3.3.3 實驗操作與檢量線配製　　　　　 43
3.3.4 空白樣本與重複性分析　　　　　 45
第四章 結果與討論　　　　　 47
4.1 定性分析　　　　　 47
4.1.1 正烷類(N-alkane)、Pristane與Phytane 　　　　　 47
4.1.2 16種多環芳香烴(PAHs)　　　　　 50
4.1.3 菲及烷基衍生物(Phenanthrene &Alkyl-Phenanthrene)　　　　　 52
4.1.4 二苯并噻吩及烷基衍生物(Dibenzothiophene & alkyl-dibenzothiophene)　　　　　 56
4.1.5 類萜烷(Terpanes)　　　　　 60
4.1.6 類固烷(Steranes)　　　　　 64
4.2 定量分析　　　　　 67
4.2.1 正烷類、Pristane與Phytane定量分析　　　　　 67
4.2.2 多環芳香烴定量分析　　　　　 71
4.2.3 Alkyl- Phenanthrene定量分析　　　　　 74
4.2.4 Dibenzothiophene& Alkyl - Dibenzothiophene定量分析　　　　　 78
4.2.5 類萜烷(Terpanes)定量分析　　　　　 82
4.2.6 類固烷(Sterane)定量分析　　　　　 86
4.3 診斷比值篩選與分析　　　　　 88
第五章 結論與建議　　　　　 97
5.1 結論　　　　　 97
5.2 建議與未來研究方向　　　　　 99

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