探討柴油風化過程中其化學指紋圖譜與生物指標特徵因子受揮發作用所造成之影響

本研究旨在探討柴油其化學指紋及生物特徵因子受揮發作用之影響，藉此了解風化柴油的特徵因子比值，以作為柴油洩漏事件上的來源鑑識與判別之參考。研究使用台灣兩大柴油生產公司(中油公司與台塑公司)的產品，以純油相柴油或受柴油污染之土壤分別進行揮發實驗。純油相的揮發風化實驗結果顯示，由於油相的風化速度極為緩慢，在經過4個月的揮發與100小時的迴旋揮發的風化反應後，其總碳氫化合物(TPHs)所受的揮發作用影響有相似的降解模式，僅碳數低者較易受到影響，而C13以後之碳數幾乎不受影響，且在n-C17/Pr和n-C18/Ph與pristane/phytane (Pr/Ph)特徵因子比值亦呈現良好線性關係。另一方面，柴油污染土壤實驗結果顯示，經過3個月的風化後，開放系統之兩家市售柴油成分中Pr/Ph比值範圍介於0.13-0.20，並且柴油中直鏈烷損失較為明顯(影響至C16)，因而影響到類異戊二烯(isoprenoids) 含量比，因此在柴油污染土壤實驗條件下，風化條件主要為揮發作用所主導，而風化程度僅屬於輕度風化。此外，本研究亦利用雙環類倍半萜烷(bicyclic sesquiterpanes)比值鑑識其柴油揮發結果，實驗結果發現，雖然中油公司或台塑公司市售柴油具有來源特性差異，但當風化作用影響至C16正烷烴時，不論是中油或台塑公司的柴油其雙環類倍半萜烷比值則無法適用。最後在分析Naphthalenes (萘系列化合物)、Fluorene (芴系列化合物)以及Phenanthrenes (菲系列化合物)之指紋圖譜，將特徵因子進行一致性評估後，結果顯示當風化作用尚未影響C11以前，其Naphthalenes、 Fluorene與Phenanthrenes之特徵因子比值均適用，但若影響至C16，則Naphthalenes與部分Fluorene系列化合物(輕質部分)則無法適用。整體而言，中油公司與台塑公司市售柴油受風化程度影響差異不大，可能為相同環境所承受之風化作用亦相同，而其中有部分的差異應為油品特性所導致。即便如此，從本研究的結果亦可得知，當油品受風化作用時，環狀脂肪烴(Cyclic Aliphatic Hydrocarbons) 和芳香烴(Aromatic Hydrocarbons)的抗風化能力明顯大於正烷烴，當風化作用影響至C16正烷烴時，則雙環類倍半萜烷與多環芳香烴中的萘系列將無法提供特徵因子比值，因此在漏油污染鑑識/評估時，如果能先確認其風化作用影響程度，則可提高判識的準確性。

關鍵字

生物標誌物；特徵因子比值；化學指紋；揮發；風化

並列摘要

The purpose of this study is to understand the effect of vaporization on the changes of diesel-chemical fingerprinting and associated biomarkers during weathering processes. In the meantime, the diagnostic ratios of difference weathered diesel-produces were also investigated for their applicability in the characterization and source identification of spilled diesel. Vaporization tests were conducted on pure-phase diesel and diesel-contaminated soil using diesel fuel obtained from CPC Corporation, Taiwan (CPC) and Formosa Petrochemical Corporation (FPCC), respectively. Results from the pure-phase diesel experiments indicated that diesel was slightly weathered after 4-month vaporization or 100-day rotation vaporization. Both brands had similar degradation patterns of total petroleum hydrocarbons (TPHs) after vaporization, showing that only carbons less than C13 were impacted and carbons raging over C13 were nearly uninfluenced. Further, significantly linear relationships were observed between the diagnostic ratios of n-C17 to Pr (n-C17/Pr), n-C18 to Ph (n-C18/Ph), and pristine to phytane (Pr/Ph). On the other hand, results from experiments of diesel-contaminated soils after 3-month weathering revealed that for both brands, the Pr/Ph ratio ranged from 0.13 to 0.20 on the open system, and significant depletion of n-alkanes diesel (carbon ranged to C16) occurred, thus influencing the content of isoprenoids. Apparently, vaporization was the key factor of weathering conditions in the diesel-contaminated soil experiments, but caused a minor effect on pure-phase diesel weathering. In summary, the overall differences of weathering diesel from either CPC or FPCC were not significantly due to the similarly wreathing conditions were conducted, and the partial difference from the experiment results were possible caused by the original source characteristics. The study results clearly indicated that the cyclic aliphatic hydrocarbons and aromatic hydrocarbons were much more resistance to the weathering conditions than the n-alkanes. When the weathering processes has an influence on n-alkanes C16, the diagnostic ratio of bicyclic sesquiterpanes and the naphthalenes of polycyclic aromatic hydrocarbons were not provide as a good biomarker. Consequently, the well evaluation of the weathering extent in the oil spilled cases is helpful to increase the accuracy of source identification and characterization.

並列關鍵字

Boimarkers ； Diagnostic Ratio ； Chemical fingerprinting ； Volatile ； weathered

參考文獻

孫培艷、高鎮會、崔文林，「油指紋鑒別技術發展與應用」，海洋出版社，北京(2007)。

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探討柴油風化過程中其化學指紋圖譜與生物指標特徵因子受揮發作用所造成之影響

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