轻质油海上溢出的化学指纹的研究
摘要
石油,在给人们带来财富和舒适生活的同时,也不可避免会给环境造成污染。随着海上石油运输量的增大,近几年来海上溢油事故频发,达到年均约500起,溢油量每年约有40万吨。溢油不仅带来严重的经济损失,更对海洋生态环境和周边海岸造成了重大的污染。因而通过研究石油的化学指纹来鉴别海上溢油的种类,并采取相应的应急措施,便成了溢油研究的重点。由于轻质油比重质油易于挥发,风化前后其组分变化比较大,因此对它的鉴别比原油更为困难些。
本研究以轻质油0#柴油和150#润滑油为研究对象,通过气相色谱仪、高效液相色谱仪、气相色谱-同位素质谱联用和原子吸收分光光度计等手段,对其风化前后的正构烷烃(nC10～nC20、姥鲛烷Pr和植烷Ph)、芳香烃(PAHs)、碳稳定同位素比δ(12C/13C)和镍钒比等一系列特征值变化的调查,以提供鉴别溢油种类的化学指纹,为识别不同种类的轻质油提供依据,丰富完善海上的溢油鉴别系统。实验结果表明,上述特征参数可以构成识别0#柴油和150#润滑油的不同化学指纹,构成柴油化学指纹的有nC15～nC24正构烷烃和类异戊二烯烃及其特征比值、碳的δ值都大于-30‰、单环芳香烃萘等；而构成润滑油化学指纹的有正构烷烃nC9～nC30、碳的δ值都小于-30‰、多环芳烃等。
本实验通过研究这些轻质油,试图找出它们的化学指纹作为海上溢油鉴定的依据,丰富完善海上溢油的鉴别系统。
Petroleum, it brings us much treasure, but also result in seriously environmental pollution problems. Petroleum transportation rapidly grow with more and more demands of all the countries, especially the maritime transportation.There is 40 tons spilling oil from shipping accidents every year, in recent years, this accidents grow up to 500 times each year. The oil splling into the sea contaminated the ocean and around the coast. So, the most effective manner is that research the chemical fingerprinter to distinguish oil type, and take all kinds of treatment measure to decrease the losses caused by oil spilling. Because of the volatility of the light oil is better than heavy oil, to distinguish the change of the component in light oil is more difficult than crude oil after weathering,
In this study,0# diesel oil and 150# lubricating oil were as the investigation object. Through the instrumental analysis such as GC, HPLC, GC-IRMS and F-AAS, we can provide the chemical fingerprints for distinguising from light oil splling, which formed by characteristic parameter such as n-alkanes (nC10-nC2o, Pr and Ph)), polycyclic aromatic hydrocarbons(PAHs), steady isotope mass ratio of carbon(13C/12C) and the ratio of nickel to vanadium(Ni/V), These supply and enrich the database of identification system for oil spilling. The experimental results show that the characteristic parameter of oil can constitute the different chemical fingerprint to distinguish the diesel and lubricating oil. To 0#diesel oil, these parameters include alkanes(nC15-nC24), isoprenoid hydrocarbons and their ratio, carbonδ(13C/12C) are more than -30%o and 1-ring aromatic hydrocanbons such as Nap,to 150# lubricating oil, these parameters contain alkanes(nC9-nC3o), carbonδ(13C/12C) are less than-30%o and the PAHs.
This study attempt to find chemical fingerprint of light oil as the basis for identification oil type, enrich and improve the identification system of oil spilling.
本研究以轻质油0#柴油和150#润滑油为研究对象,通过气相色谱仪、高效液相色谱仪、气相色谱-同位素质谱联用和原子吸收分光光度计等手段,对其风化前后的正构烷烃(nC10～nC20、姥鲛烷Pr和植烷Ph)、芳香烃(PAHs)、碳稳定同位素比δ(12C/13C)和镍钒比等一系列特征值变化的调查,以提供鉴别溢油种类的化学指纹,为识别不同种类的轻质油提供依据,丰富完善海上的溢油鉴别系统。实验结果表明,上述特征参数可以构成识别0#柴油和150#润滑油的不同化学指纹,构成柴油化学指纹的有nC15～nC24正构烷烃和类异戊二烯烃及其特征比值、碳的δ值都大于-30‰、单环芳香烃萘等；而构成润滑油化学指纹的有正构烷烃nC9～nC30、碳的δ值都小于-30‰、多环芳烃等。
本实验通过研究这些轻质油,试图找出它们的化学指纹作为海上溢油鉴定的依据,丰富完善海上溢油的鉴别系统。
Petroleum, it brings us much treasure, but also result in seriously environmental pollution problems. Petroleum transportation rapidly grow with more and more demands of all the countries, especially the maritime transportation.There is 40 tons spilling oil from shipping accidents every year, in recent years, this accidents grow up to 500 times each year. The oil splling into the sea contaminated the ocean and around the coast. So, the most effective manner is that research the chemical fingerprinter to distinguish oil type, and take all kinds of treatment measure to decrease the losses caused by oil spilling. Because of the volatility of the light oil is better than heavy oil, to distinguish the change of the component in light oil is more difficult than crude oil after weathering,
In this study,0# diesel oil and 150# lubricating oil were as the investigation object. Through the instrumental analysis such as GC, HPLC, GC-IRMS and F-AAS, we can provide the chemical fingerprints for distinguising from light oil splling, which formed by characteristic parameter such as n-alkanes (nC10-nC2o, Pr and Ph)), polycyclic aromatic hydrocarbons(PAHs), steady isotope mass ratio of carbon(13C/12C) and the ratio of nickel to vanadium(Ni/V), These supply and enrich the database of identification system for oil spilling. The experimental results show that the characteristic parameter of oil can constitute the different chemical fingerprint to distinguish the diesel and lubricating oil. To 0#diesel oil, these parameters include alkanes(nC15-nC24), isoprenoid hydrocarbons and their ratio, carbonδ(13C/12C) are more than -30%o and 1-ring aromatic hydrocanbons such as Nap,to 150# lubricating oil, these parameters contain alkanes(nC9-nC3o), carbonδ(13C/12C) are less than-30%o and the PAHs.
This study attempt to find chemical fingerprint of light oil as the basis for identification oil type, enrich and improve the identification system of oil spilling.
引文
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[2]王丽,卓林,何鹰,等.近红外光谱技术鉴别海面溢油.光谱学与光谱分析,2004,24(12)：1537-1539
[3]范志杰,宋春印,等.海洋溢油的风化过程及其对环境的影响.油气田环境保护,1996,6(1)：54-57
[4]吕馨.海洋中重度风化溢油指纹鉴别技术的研究：[硕士学位论文].大连：大连海事大学环境科学与工程学院,2004
[5]孙培艳,包木太,王鑫平,等.国内外溢油鉴别及油指纹库建设现状及应用,西安石油大学学报(自然科学版),2006,21(5)：72-76
[6]罗霞.海面溢油油指纹分析鉴定研究：[硕士学位论文].青岛：中国海洋大学环境科学与工程学院,2007
[7]陈伟琪,张珞平,鉴别海面溢油的正构烷烃气相色谱指纹法,台湾海峡,第21卷第三期,2002年8月
[8]吕振波,田彦文,庄丽宏等,高效液相色谱法在石油及其产品中的应用,四川化工,第8卷,2005年第1期：35-38
[9]严志宇,殷佩海,溢油风化过程研究进展,海洋环境科学,第9卷第一期,2000年2月
[10]张建民,杨惠芳,李更辰,王永强,用石墨炉原子吸收光谱法测定润滑油中的痕量镍,分析仪器,2003,2.34—35
[11]Z D wang, M Fingas. development of oil hydrocarbon fingerprinting and identification techniques. Marine Pollution Bulletin.2003,47:423-452
[12]王传远,杜建国,贺世杰.海洋溢油的风化过程研究.海洋湖沼通报,2008,(3)：79—83
[13]Smith J E, Torrey Canyon. Pollution and marine life. London:Cambridge University Press,1996
[14]孙培艳,高振会,崔文林等.油指纹鉴别技术发展及应用.北京：海洋出版社,2007.
[15]文强.原油混合油指纹鉴别分析：[硕士学位论文].青岛：中国海洋大学应用化学系,2007
[16]包木太,文强,崔文林,等.六种成品油的正构烷烃色谱指纹提取与鉴别.西安石油大学学报(自然科学版),2007,22(1)：87～90
[17]P. S. Daling, Faksness, L. G., Hansen, A. B., Stout. S. A., Improved and standardized methodology for oil spill fingerprinting. In:Proceedings of the 25th Arctic and Marine Oil Spill Program (AMOP) Technical Seminar, Environment Canada, Ottawa,2002: 429-454.
[18]徐广通,刘泽龙,杨玉蕊等.近红外光谱法测定柴油组成及其应用.石油学报：石油加工,2002,18(4)：65—71
[19]刘慧颖,韦锐,熊春华.用傅里叶变换红外光谱测定汽油有关性质.分析化学,2001,29(6)：7312734
[20]陈淑梅,赵云英.影响荧光法鉴别海面溢油的各种因素研究.大连水产学院学报,2000,15(1)：35—40
[21]陈伟琪,张骆平,气相色谱指纹法在海上油污染源鉴别中的应用.海洋科学,2003,27(7)：67—70.
[22]Z. D. Wang, Merv Fingas, and Ken Li, Fractionation of a light crude oil and identification and Quantitation of Aliphatic, Aromatic, and Biomarker compounds by GC-FID and GC-MS, part I, Journal of Chromatographic Science, Vol.32,1994.
[23]吕振波,田彦文,庄丽宏等.高效液相色谱法在石油及其产品中的应用.四川化工,2005,8(1)：35—38
[24]徐恒振,周传光,马永安,等.特种生物标志物作为溢油指示物(或指标)的研究.交通环保,2001,22(6)：5—11
[25]Z. D. Wang, Fingas, M., Landriault, M., Sigouin, L., Castle, B., Hostetter, D., Zhang, D., Spencer, B., Identification and linkage of tarballs from the coasts of Vancouver Island and Northern California using GC/MS and isotopic techniques. J. High Resolut. Chromatogr.21,1998:383-395
[26]Z. D. Wang, Fingas, M., Use of methyldibenzothiophenes as markers for differentiation and source identification of crude and weathered oils. Environ. Sci.Technol.29 (11),1995:2841-2849
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