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将胜利和塔西两种原油以不同比例混合后置于人工气候箱进行风化模拟实验,采用气相色谱质谱联用仪(GC-MS)检测风化样品中的生物标志化合物,探讨和揭示短期风化作用对混合溢油常用的甾萜类和多环芳烃诊断指标的影响。结果表明经过15d的短期风化,在混源比例大于10%时,各系列混合油样的甾萜类生物标志物诊断指标与单一油品的相关诊断比值的差异性和混源油品比例值呈明显正相关。各系列混合油样中的常用萘及烷基萘等指标不适宜作为短期溢油来源鉴别的指标,但可以作为溢油是否发生混合的间接判定指标。根据常用的多环芳烃相关诊断指标,可将各系列油样的短期风化模式依据混源油品中塔西油田原油所占比例大致分为3类(20%~50%、10%和0%)。多环芳烃系列诊断指标的相对标准偏差(RSD%)与混源油品比例有关,混源塔西油样的比例越高,PAHs系列指标的RSD%越大,稳定性越差。 相似文献
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多环芳烃油指纹应用于船舶溢油鉴别研究 总被引：2，自引：0，他引：2
溢油种类主要包括船舶燃料油和原油,二者性质的差异决定了鉴别方法也相应不同,寻求适合于船舶溢油的鉴别方法具有重要意义。在使用柱色谱层析方法对样品进行分离前处理的基础上,以气相色谱/质谱方法(GC-MS)为主要分析手段,对溢油样品和可疑船舶溢油源样品的多环芳烃油指纹特征进行对比,并在多环芳烃油指纹参数的基础上进一步进行多环芳烃内组成三角图分布特征与聚类分析研究,成功为珠江口水域某船舶溢油事故追踪到肇事溢油源。结果表明:取自丁船的油样和现场溢油样芳烃油指纹特征最为相近,是此次溢油事故的溢油源。受风化作用后的船舶燃料油中饱和烃类化合物数量稀少,且含量极低,不适合用于溢油鉴别,而多环芳烃类化合物较饱和烃类化合物而言具有含量高、种类丰富的特点,是该类溢油鉴别的主要油指纹依据。使用油指纹参数进行可疑溢油源识别时,充分考虑油品中有机分子所受风化影响程度的不同是风化条件下溢油鉴定的关键。因此,多环芳烃油指纹可以有效应用于船舶燃料油溢油的鉴别。 相似文献
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通过自然条件下沙表层和水面溢油的模拟风化实验,采用GC-MS作为检测器,研究原油中的正构烷烃在厦门地区的风化规律.结果表明,在一个月的风化模拟实验中,两种不同介质溢油风化均明显体现轻组分的正构烷烃丢失现象,且正构烷烃组分在水面溢油的风化速率低于沙表层溢油速率1～2个碳数.沙上模拟实验后期APr/APh比值明显受到风化影响,诊断比值不适用于油源鉴别.诊断比值An-C17/APr、An-C18/APh在短期风化过程中受风化影响小.水面溢油模拟实验结束后发现水体中n-C13-n-C29的正构烷烃组分含量升高2.9%～327.4%. 相似文献
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基于特征比值的原油中PAHs标志物风化规律研究 总被引：1，自引：1，他引：0
以渤海某原油作为研究对象进行综合模拟风化实验, 探讨了原油中五类PAHs组分的风化规律并筛选出其中稳定的诊断比值。结果表明: 经过50d风化, 原油中PAHs的分布已经发生了较大的改变, 其中萘系类损失最为严重, 菲系列所占的比例有所提高, 二苯并噻吩、屈、芴系列则保持相对稳定, 这为进一步筛选用于溢油来源鉴别的新诊断比值参数提供了一定依据; 经风化检验, 现有常用6种PAHs诊断比值在风化50d后较稳定, 可用于风化溢油的鉴别; 所选取新诊断比值中, 菲和屈系列、烷基取代二苯并噻吩类、烷基取代芴类抗风化能力较强, 共筛选出34种诊断比值可作为溢油鉴别的有效指标。 相似文献
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以燃料油为研究对象进行室外自然风化实验(0~100 d),探讨了含硫多环芳烃的风化规律。研究结果表明:燃料油中二苯并噻吩系列化合物的分布特征保持相对稳定,苯并[b]萘[2,1-d]噻吩在短期风化时间内(0~45 d),其相对丰度相对稳定,经过100 d的风化,相对丰度逐渐降低。通过重复性限判别方法,13个含硫多环芳烃诊断比值在风化60 d内基本稳定,可以用于指示风化60 d内油样是否同源,诊断比值1-MDBT/DBT、C0-BNT/2-+3-MDBT、C0-BNT/1-MDBT和C3-DBT/C3-BNT在风化100 d内不稳定,不适用于60~100 d风化油品鉴定。 相似文献
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通过对具有代表性的两种原油和两种船用燃油进行340 d的室外模拟风化模拟实验,运用GC-FID法和同步荧光光谱法对海水中风化的漂浮油和沉底油的特性进行分析,为沉底油溯源提供相关依据,以此完善海上溢油事故的监管工作。结果表明:4种实验油品的漂浮油和沉底油荧光光谱差别不大,因此可以用荧光光谱法初步测定沉底油的风化时间;沉底油受蒸发、光解等影响弱于漂浮油,其GC可保持低碳组分峰形,并且由于生物降解,沉底油的气相谱图中均出现不可分辨的复杂混合物(UCM)的特征图谱,可以作为判断是否沉底的判据;两种方法相结合,可以建立一种确定溢油时间、风化经历及方法,以便对溢油进行更准确的溯源。 相似文献
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荧光光谱具有灵敏度高、选择性好、分析速度快等特点被广泛应用于溢油鉴别。通过结合同步荧光光谱法、导数荧光光谱法和三维荧光光谱法对某码头一次溢油事故的溢油样进行分析鉴别,快速准确地鉴别出溢油源,进一步说明了荧光光谱法是溢油鉴别中一种有效的技术方法。研究结果表明:(1)同步荧光光谱对油源较为相近的油样区分能力较差,但可初步判断其相似性;(2)三维荧光光谱图油样荧光强度会受风化等因素的影响,但谱图的整体轮廓受干扰因素影响较小,芳烃的测定结果能比较准确地反映出溢油源的特征信息;(3)一阶导数荧光光谱中峰的比值能增强光谱特征,提高溢油鉴别的分辨能力。 相似文献
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本文利用采集于我国三大油田的五种原油样品开展了长达210天的溢油风化模拟实验,并依据相对偏差和重复性限数学分析法,进行溢油风化过程分析和诊断比值应用效果评估。研究结果表明:经过210天的风化,溢油鉴定诊断比值发生明显改变;其中来源于萜烷、甾烷和多环芳烃的诊断比值变化率要远低于正构烷烃,可用于中长期风化溢油鉴定。此外,研究发现,在这些有效诊断比值中有4个变化率较小,相对偏差低于5%,保持了较好的稳定性,更适合于重度风化溢油鉴定。 相似文献
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Bicyclic Sesquiterpanes (BSs) are ubiquitous components of crude oils and ancient sediments. BSs in crude oils and diesel oil were identified and characterized, the effects of moderate weathering on BS distributions were discussed, and a methodology using diagnostic indices of BSs was developed for oil correlation and differentiation. The results showed that crude oils and oil products had different abundances and distributions of BSs and, consequently, resulted in different diagnostic ratios. The selected diagnostic ratio indices of BSs, such as BS4/BS5 (ratio of 4,4,8,9,9-pentamethyl-decahydronaphthalene to 8β (H)-drimane), BS6/BS5 (ratio of 4,4,9,9,10-pentamethyl-decahydronaphthalene to 8β (H)-drimane), BS8/BS9 (ratio of the second peak to the third peak of C 16 sequiterpane), and BS8/BS10 (ratio of C 16 sequiterpane to 8β (H)-homodrimane), still maintained better stabilities (%RSD < 5%) after weathering for 30 d. The longer weathering process (150 d) had some effect on such ratios (5% < %RSD < 10%). The facts of the uniqueness, abundance in petroleum, and chemical stability of BSs enable them to be suitable as an effective diagnostic means for identifying spilled oil with moderate weathering, particularly for lighter refined product samples that are difficult to identify by current techniques. 相似文献
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Sixty crude oils from the Termit Basin (Eastern Niger) were analysed using biomarker distributions and bulk stable carbon isotopic compositions. Comprehensive oil-to-oil correlation indicates that there are two distinct families in the Termit Basin. The majority of the oils are geochemically similar and characterized by low Pr/Ph (pristane to phytane ratios) and high gammacerane/C30 hopane ratios, small amounts of C24 tetracyclic terpanes but abundant C23 tricyclic terpane, and lower δ13C values for saturated and aromatic hydrocarbon fractions. All of these geochemical characteristics indicate possible marine sources with saline and reducing depositional environments. In contrast, oils from well DD-1 have different geochemical features. They are characterized by relatively higher Pr/Ph and lower gammacerane/C30 hopane ratios, higher amounts of C24 tetracyclic terpane but a low content of C23 tricyclic terpane, and relatively higher δ13C values for saturated and aromatic hydrocarbon fractions. These geochemical signatures indicate possible lacustrine sources deposited under freshwater, suboxic-oxic conditions. This oil family also has a unique biomarker signature in that there are large amounts of C30 4α-methylsteranes indicating a freshwater lacustrine depositional environment.The maturity of the Termit oils is assessed using a number of maturity indicators based on biomarkers, alkyl naphthalenes, alkyl phenanthrenes and alkyl dibenzothiophenes. All parameters indicate that all of the oils are generated by source rocks within the main phase of the oil generation stage with equivalent vitrinite reflectance of 0.58%–0.87%. 相似文献
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以柴油为研究对象,采用溢油风化模拟实验,从分子级水平揭示中长期风化作用对溢油组成的影响。利用相对偏差和重复性限法进行评价和筛选,研究表明,柴油在较短时间(10 d)内,phytane/n-C18和pristine/phytane特征比率可较好地作为油品鉴别的依据;在10~30 d的风化期间,pristine/phytane仍可作为油品鉴别的依据;较长期的风化过程后,上述三个正构烷烃特征比率对于油品鉴别已不再具备意义。所选多环芳烃诊断比值指标中,除MNR、MP/P外,其他参数(MPI-1,MPI-2,Rc,MPDF1,MPDF2,MNR)相对标准偏差在1.10%~5.40%,可较好地用于重度风化溢油源鉴定。 相似文献
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Crude oil samples from Cretaceous and Tertiary reservoir sections in the Zagros Fold Belt oil fields, southern Iraq were investigated using non-biomarker and biomarker parameters. The results of this study have been used to assess source of organic matter, and the genetic link between oils and their potential source rocks in the basin. The oils are characterized by high sulphur and trace metal (Ni, V) contents and relatively low API gravity values (17.4–22.7° API). This indicates that these oils are heavy and generated from a marine source rock containing Type II-S kerogen. This is supported by their biomarker distributions of normal alkanes, regular isoprenoids, terpanes and steranes and the bulk carbon isotope compositions of their saturated and aromatic hydrocarbons. The oils are characterized by low Pr/Ph ratios (<1), high values of the C35 homohopane index and C31-22R/C30 hopane ratios, relatively high C27 sterane concentrations, and the predominance of C29-norhopane. These biomarkers suggest that the oils were generated predominantly from a marine carbonate source rock, deposited under reducing conditions and containing plankton/algal and microorganisms source input. The presence of gammacerane also suggests water column stratification during source rock deposition.The biomarker characteristics of the oils are consistent with those of the Middle Jurassic Sargelu carbonate as the effective source rock in the basin. Biomarker maturity data indicate that the oils were generated from early maturity source rocks. 相似文献
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Geochemical as well as multivariate statistical analyses (PCA) were carried out on 20 crude oil samples from ‘Middle’ Pliocene Production Series (MPPS) of Guneshli-Chirag-Azeri (GCA), Bahar, and Gum Adasi fields in the western South Caspian Basin (SCB). PCA analysis employed to source-specific biomarkers distinguishes the oils into two types one being divided into two sub-types; Type 1 (GCA oils), Type 2A (Bahar field oils) and Type 2B (Gum Adasi field oils). Indirect oil-to-source rock correlations to available source rock data from previous studies suggest that Type 1 oils, located in the Apsheron-Balkhans uplift area, are derived from basinal shales of the Oligocene-Lower Miocene Middle Maikop Formation. Type 2A and 2B oils, located in the Gum-deniz-Bahar-Shakh-deniz trend area, are more likely derived from shelf-edge shales of the Upper Maikop Formation and the Middle-Upper Miocene Diatom Suite, respectively.Biomarker maturity study reveals that Type 1 oils (mean %Rc=0.78) are more mature than Type 2 oils (mean %Rc=0.71). Source rocks, which generated these oils, were at generation depth interval between 5200 m (112 °C) and 7500 m (153 °C) at the time of expulsion. This indicates that the western SCB oils experienced significant long-range vertical migration along the deep-seated faults to accumulate in the MPPS reservoirs. Post-accumulation biodegradation process was only observed in the Guneshli field where bacterial alteration (level 4) began between 4.2 and 2.6 mybp and stopped with the deposition of the overlying impermeable Upper Pliocene Akchagyl Formation. Subsequent light hydrocarbon (C1–C16) charge into the Guneshli fields caused precipitation of asphaltenes, which is evidenced by high resin to asphaltene ratios for the present-day Guneshli oils. Evaporative-fractionation examined using the scheme of [Thompson, 1987] showed high correlations of the ‘aromaticity’ B parameter (=toluene/n-C7) and ‘parafinicity’ F parameter (=n-C7/MCH with the %Rc (maturity) and C27/C29 sterane ratio (organic matter type). This implies that Thompson's approach should be used with caution in the SCB. Among the several mechanisms, rapid and thick deposition of Pliocene sediments and subsequent high heating rate on the Maikop Formation and Diatom Suite is probably the most plausible way of explaining the origin of light hydrocarbons in the Guneshli and Bahar fields. 相似文献
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《Marine and Petroleum Geology》2012,33(1):138-158
Different methods have been used to examine minerals and/or solid bitumens in three adjacent Carpathian regions of Poland, Ukraine and Slovakia. The minerals fill smaller and larger veins and cavities, where they occur either together or separately. They usually co-occur with the solid bitumens. All δ13CPDB values measured for calcite lie in a relatively wide interval between −6.25‰ and +1.54‰, while most values fall into the narrower interval from below 0 to about −3‰. The general range of calcite δ18O results for the whole studied region is between +17.13‰ and +25.23‰ VSMOW or from about −11 to −5‰ VPDB, while the majority of these values are between +20.0 and 23.5‰ VSMOW (−10.53 and −8.00‰ PDB, respectively). δ18OVSMOW results for quartz vary between +23.2 and 27.6. The carbonate percentage determined in some samples falls between from <2% CaCO3 to >90% CaCO3, while the TOC values changes from 0.09% to over 70%.The aliphatic fraction predominates in all studied samples, mainly in bitumens and oils. The composition of the aliphatic fraction is relatively homogeneous and points to a strong aliphatic, oil-like paraffin character of the bitumens. Such a composition is characteristic of the Carpathian oils and different from the rocks studied that contain the higher percentage of a polar fraction. The content of the aliphatic fraction in bitumens is only slightly higher than that in two oils used for comparison. The distribution of n-alkanes is variable in rocks, solid bitumens as well as inclusions in quartz and calcite. Two groups of bitumens may be distinguished. Those with a predominance of long-chain n-alkanes in the C25–C27 interval (in some cases from C23–C25 and without or with a very low concentration of short-chain n-alkanes in the interval of C14–C21) show also a high content of isoprenoids i.e. of pristane (Pr) and phytane (Ph). In all but one bitumen samples, Pr predominates over Ph. The second group comprises oils and rock samples with a characteristic predominance of short-chain n-alkanes in the interval from C13–C19 and a low percentage of the long-chain n-alkanes from the n-C27–n-C33 interval. Pristane and phytane exhibit a concentration comparable to that of C17 and C18 n-alkanes with a Pr predominance over Ph. Due to high maturity, only small amounts of the most stable compounds from the hopane group have been observed in the samples, also oleanane in one case. Among the aromatic hydrocarbons, phenanthrene and its methyl- and dimethyl-derivatives are dominant in bitumens, source rocks and inclusions in calcite and quartz. Occurrence of cyclohexylbenzene and its alkyl-derivatives as well as cyclohexylfluorenes in solid bitumens suggest that they formed from oil accumulations under the influence of relatively high temperatures in oxidizing conditions.Homogenization temperatures for aqueous/brine inclusions in quartz within the Dukla and Silesian units (Polish and Ukrainian segments) are between 125 and 183.9 °C, while salinities are low in the interval of 0.2–5.5 wt% NaCl eq. The inclusions in calcite homogenize at higher temperatures of almost 200 °C and the brine displays higher salinity than the fluid in the quartz. Two quartz generations may be distinguished by inclusion and isotope characteristics and the macroscopic diversity. Oil inclusions homogenize at 95 °C. One phase inclusions in quartz contain methane, CO2 and nitrogen in variable proportions. 相似文献
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采用气相色谱法对渤海海上6个不同区块、7个平台的8口油井原油中正构烷烃组分及姥鲛烷植烷进行了定性定量分析,通过原始指纹谱图、正构烷烃组分及姥鲛炕植烷浓度分布比较和特征比值比较对原油进行了鉴别.结果表明,不同区块的原油指纹信息不尽相同,即使同一平台不同油井所产的原油指纹也存在一定差异,采用气相色谱法进行分析可对其进行鉴别.原油的风化对特征比值影响较小,可利用其进行风化油样的鉴别.为确保鉴别的准确性,分析过程中必须实施严格质量控制措施. 相似文献