海洋风化溢油鉴别中特殊芳烃标志物的应用

对母质来源、沉积环境和成熟度各异的原油样品进行风化模拟实验,并对实验产物进行GC-MS分析,最后基于油气地球化学手段对多环芳烃风化溢油鉴别的可行性、原理、常用指标等进行探讨,结果表明,不同油样中同一芳烃生物标志化合物比值参数鼍值问有显著性差异;对同一油样的风化和未风化样品而言,同一烷基化多环芳烃特征比值参数的变异系数为6.51%-17.68%,而成熟度指标的变异系数通常小于8%;芳烃中烷基萘和"三芴"的分布特征、甲基萘指数、甲基菲指数和烷基化多环芳烃同系物的双比率可以作为重风化溢油鉴别的有效指标.     

岸滩模拟溢油生物降解条件下原油中双环倍半萜变化规律

以渤西油田海上平台中质原油作为研究对象,进行岸滩模拟溢油生物降解实验.采用气相色谱与质谱联用技术(GC-MS)对原油中双环倍半萜化合物进行了分析,探讨了不同生物降解条件下双环倍半萜化合物的分布规律,并对该化合物诊断比值的变化规律以及稳定性进行了考察.研究结果表明,经过21 d的生物降解,加入生物降解菌剂和营养盐的原油中双环倍半萜化合物的分布变化不大,加入生物降解菌剂和缓释肥的原油中双环倍半萜化合物降解比较大.经过t检验分析,经过21 d短期生物降解,双环倍半萜化合物诊断比值DR3、DR6、DR9以及DR10,可以用于判别生物降解前21 d内油样是否来自同一油源.双环倍半萜化合物诊断比值对于溢油来源鉴别具有重要意义.     

用正构烷烃分布特征鉴别海上混合原油

为鉴别海上混合型溢油,对混合原油的正构烷烃分布特征进行探讨,通过混油实验考察混合比对正构烷烃分布以及诊断比值的影响.实验中正构烷烃分布相异最大的大庆原油和沙特原油混合后,n-C_(10)—n-C_(18)的相对含量与大庆原油比例呈线性负相关,而n-C_(18)—n-C_(35)与其呈线性正相关,这种双向分布的特点明显不同于单油的单向分布.正构烷烃分布相近的阿联酋-伊拉克混油中n-C_(10)—n-C_(35)分布与单油几乎相同,但其n-C_(18)/Ph随着混合比而变化,据此可以判别是混油还是单油.混合原油的n-C_(17)/Pr、n-C_(18)/Ph和Pr/Ph取决于单油之间的差异性,相差较大的混合后与混合比呈线性相关.30 d短期风化实验表明,混油中的n-C_(10)—n-C13受风化影响下降明显,而n-C15—n-C_(35)变化不大.混合原油的n-C_(17)/Pr、n-C_(18)/Ph和Pr/Ph基本上不受风化影响,即诊断比值仍可作为鉴别风化混油种类的依据.     

液相色谱稳定特征峰比值鉴别模拟渤海溢油

考察室外自然风化对原油液相色谱稳定特征峰分布的影响,提出基于溢油液相色谱稳定特征峰比值结合聚类分析和"t-检验"分析进行模拟溢油鉴别.结果表明,液相色谱稳定特征峰比值结合聚类分析可以初步推测模拟溢油样品来源,进一步采用特征峰比值和"t-检验"分析可以实现模拟溢油样与可疑原油样品的成功判别.     

利用GC和GC/MS对溢油风化的鉴定

对重质燃料油泄漏两个月后现场采集的溢油样品进行分析,通过对比可见:各样品的风化程度不一,碳数较低的烷烃明显减少,特征比值C19 20/C21 22和Pr/Ph较为稳定,能很好地指示油样的来源;但C17/Pr和C18/Ph已明显降低.通过对1*油样与泄漏的重质燃料油中芳烃比较可知:芳烃CnB,C0N,C1N,C2N和C3N基本消失,油样与泄漏的重质燃料油中C3D(m/z 226)的分布几乎完全一致,说明C3D的分布对溢油鉴定有十分重要意义.     

典型消油剂对溢油鉴别生物标志物指示作用的影响

在一定条件下,分别对添加消油剂的原油和重质燃料油进行了风化模拟实验,采用气相色谱质谱联用(GC-MS)对风化样品中的生物标志化合物进行了检测,通过生物标志化合物特征比值的变化趋势,对以往溢油鉴别过程中常规生物标志化合物特征比值进行筛选.结果表明,在溢油经消油剂处理后,以往经常选用的指纹信息(主峰碳数、CPI、(C21+C22)/(C28+C29)、C21前/C22后、Pr/Ph(姥鲛烷/植烷)、Pr/C17、Ph/C18)受到消油剂中相关组分的干扰,失去指示意义;消油剂加剧了某些多环芳烃及其烷基化系列生物标志化合物的风化作用,使与其相关的生物标志化合物比值(C2-D/C2-P、C3-D/C3-P、ΣP/ΣD、2-MP/1-MP、4-MD/1-MD)失去指示意义;绝大部分甾、萜烷类生物标志化合物的抗风化能力较强,相关比值仍具有较好的指示意义.     

海面溢油样品指纹解析

在2010年7月16日大连输油管道爆炸事故发生后,在24 h内分别于事故油罐、不同海面厚油膜区域采集原始油样及溢油样品;采用气相色谱质谱联用(GC-MS)对样品中的生物标志物进行检测,通过生物标志物特征比值的变化趋势,对以往溢油鉴别过程中常规生物标志物特征比值进行评价和筛选,并对溢油样品的指纹特征和风化规律进行解析.溢油样品的分析结果表明,在多种因素共同作用的不超过24 h的短期风化过程影响下,筛选排除的生物标志物比值均为国标GB/T 21247—2007中建议的nC17/Pr、nC18/Ph特征比值.化学消油剂与生物消油剂的盲目使用,有可能导致溢油指纹特征的显著变化.     

原油及石油炼制品指纹特征差异性研究

采用气相色谱质谱联用方法(GC/MS),对原油及石油炼制品(包括柴油、机油、燃料油)进行了指纹图谱分析.通过对4种油品中烷烃类、生物标志物和多环芳烃类化合物的原始图谱及半定量浓度和诊断比值比对分析.结果显示,4种油品相互之间烷烃类化合物图谱具有明显差异,机油存在明显UCM(不可分辨的混合物)"鼓包",在n C17/Pr、n C18/Ph、n C17/n C18、Pr/Ph和(n C19+n C20)/(n C19+n C20+n C21+n C22)特征比值上存在显著性差异.4种油品在甾烷类、三芳甾烷类、萜烷类和藿烷类化合物的分布和含量上差异性明显;在多环芳烃化合物的含量和分布上,差异不明显.所选取的29个生物标志物特征比值,其中13.79%的特征比值可体现原油、柴油、机油、燃料油的差异性,可作为原油与石油炼制品之间油种鉴定的重点筛查指标.     

烃类污染物在大气气溶胶源解析方面的应用

分析了国内外的资料,并结合几年来对北京地区的研究成果,讨论了饱和烃、多环芳烃等有机污染物在源解析方面的应用。利用饱和烃进行源解析主要依靠正构烷烃的分布特征和主峰碳、CPI、OEP等参数,以及姥鲛烷和植烷的Pr/Ph、Pr/C17、Ph/C18比值;甾烷及萜烷等环状化合物,性质非常稳定,可以作为化石燃料燃烧的有机示踪物。通常情况下,不同来源的多环芳烃,Ant/Phe、Flua/Pyr、BaA/Chr等比值有一定的差别;因此这些比值也可以作为重要的诊断参数。     

长岛岸滩及岩石附着油污指纹特征比对

选择长岛典型的两个旅游景点的岩石和岸滩附着的8个溢油样品,对样品中的饱和烷烃、萜烷、甾烷及多环芳烃化合物的分布特征及典型生物标志物诊断比值进行了比对分析.t检验结果表明,置信度为95%时,8个油样的生物标志物诊断比值指标均不能够完全匹配,不可判定其来自同一油源.九丈崖溢油样品之间差异性高于月牙湾.可见,长岛九丈崖岩石和月牙湾岸滩附着溢油样品之间具有较大相似度,但指纹特征各不相同,部分样品差别较大,具有混合油的指纹特征,为多次溢油的混合油样.     

Stimulation and inhibition of phytoplankton growth by low molecular weight hydrocarbons

Experiments on 4 phylogenetically different phytoplankton exposed in culture to a range of concentrations of benzene, toluene and xylene showed a variety of growth responses for marine microalgae. The degree of influence of these aromatic hydrocarbons, all components of fuel oils and crude oils, varied with concentration, compound and species. Stimulation of growth in Dunaliella tertiolecta resulted from low μg/l concentrations of all three compounds, Skeletonema costatum showed no growth enhancement, while Cricosphaera carterae and Amphidinium carterae were intermediate in their reactions. Closed culture vessels were found to be necessary to retain these volatile hydrocarbons. Many of the previous laboratory studies on oil using standard methods — cotton plugs, screw caps or beakers — have overlooked the important influence of the volatile fraction. The species-specific stimulation of low concentrations was further shown in experiments with mixtures of No. 2 fuel oil. The volatile fraction was most biologically reactive, being the source of growth enhancement at low levels and a major growth inhibitor at high concentrations. Thus, a significant environmental effect of oil on marine primary production could be the growth stimulation of particular species by low molecular weight aromatic compounds resulting in an alteration of the natural phytoplankton community structure and its trophic relationships.     

Investigation of the sources of aliphatic hydrocarbons in the mussel Mytilus edulis from north sea oil production platforms by Capillary glc and CGCMS†

Aliphatic hydrocarbons isolated from mussels collected over a 20 month period from three North Sea Forties field oil production platforms have been examined by capillary gas chromatography and gas chromatography‐mass spectrometry.

The biological hydrocarbons consist predominantly (300–700 μh g^‐1 lipid) of C₃₁ and C₃₃ n‐alkenes with 2, 3 and 4 double bonds probably derived from a dietary intake of Emiliania huxleyi, a microscopic coccolithophorid alga. In some of the mussels C₁₈, C₂₀ and C₂₂ n‐alkanes are present in unusually high abundance compared to their odd carbon number homologues. Possible reasons for this distribution are discussed.

The concentrations of fossil fuel hydrocarbons (mainly unresolved complex mixtures) in the mussels ranged from 330 to 5,298 μg g^‐1 of lipid. No significant increase in values was detected two months after the start of discharge of treated Forties production water from the Forties D platform.

To determine the pollutant hydrocarbon sources, the sterane and terpane distributions of hydrocarbon fractions isolated from the mussels and from a number of fossil fuels, including Forties crude oil, were examined by mass fragmentography. The steranes in the mussels from the Forties C and D platforms contained higher proportions of regular 14α(H), 17α(H) components than Forties oil in which the steranes were mainly 13ß(H), 17α(H) diasteranes. In addition, the terpane distributions of the mussel fractions differed markedly from that of Forties crude oil, particularly in the relative abundance of diterpanes to triterpanes, which was higher in the mussel fractions than in the oil, and in the absence of 17α(H), 18α(H), 21ß(H)‐18, 30‐bisnorhopane, a known component of Forties crude. Furthermore, the ratio of C₂₉ to C₃₀ triterpanes was greater than unity in the mussels but much less than unity in the Forties oil. These data preclude Forties or other similar North Sea crudes as the major source of pollutant aliphatic hydrocarbons in the mussels. The relative concentrations and distributions of steranes and triterpanes suggest that the most likely source of pollutants is a Middle Eastern based oil derived either from rig activities, or from background pollution in the North Sea. The low concentration of ≥ C₂₇ steranes in the more polluted mussels (e.g. Forties B; UCM > 200 ppm dry wt.) suggests that gas oils used on the platforms may be the major source of petrogenic hydrocarbons in these samples.     

Methodology and measurement of adenylate energy charge ratios in environmental samples

A method for measuring ATP, ADP and AMP levels in environmental samples was devised, and applied to seawater and bacterial cell extracts. This procedure is specifically designed for measuring the extremely low concentrations of total adenine nucleotides ([A_T]=[ATP]+[ADP]+[AMP]) that are apt to occur in most natural ecosystems (i.e., 10 ng A_T ml^-1 of sample extract). Although the current assay methodology can be used with purified firefly luciferase reagents, it has been suitably modified to accept crude luciferase preparations as well. ATP, ADP and AMP levels have been measured, and the corresponding energy charge (EC) ratios determined for seawater samples collected off the Southern California coast. The EC ratios ranged from 0.50 to 0.89, with peak values corresponding to the subsurface maxima in ATP and chlorophyll a concentrations, and the minimum values corresponding to the deepest water sampled (1500 m). The measurement of adenylate energy charge ratios in environmental samples can be a useful indicator of mean community metabolic activity and potential for cell growth.     

Application of an odd/even predominance of n-alkanes in oil–source rock correlation: taking the lower Paleozoic strata of the Tarim Basin as an example

The composition and distribution of n-alkanes carbon numbers reflect the source of kerogenic organic matter, sedimentary environment, and maturity of the rocks. The comparison results of the n-alkanes GC (gas chromatography) chromatograms in the Tazhong Low Uplift show that the n-alkanes of the source rocks in Upper Ordovician display an odd carbon number predominance. At the same time, Cambrian–Lower Ordovician exhibit an even carbon number predominance. The correlation between oil and source rock illustrates that crude oils in the fields of well TZ10-12 and well TZ24 stem from the Upper Ordovician source rocks. The origins of the crude oils in the fields of well TZ161-162 and well TZ45 are Cambrian–Lower Ordovician. The strata corresponding to the crude oils with odd/even carbon number predominance match the oil–source rock correlation. Thus, the characteristics of odd/even carbon number predominance in n-alkane compounds are effective for oil–source rock correlation in the Tazhong Low Uplift, Tarim Basin.     

Organic composition in the dry season rainwater of Guangzhou, China

This paper reports the results from a study of the organic composition of rainwater collected at Tianhe district of Guangzhou city, P.R. China, during the dry season. Several special setups of a pyrex bottle with a glass funnel were used for the collection of the rainwater. Three fractions (aliphatics, PAHs and fatty acids) were separated from the total extracted organic compounds and identified with GC-MS. The molecular diagnostic ratios were utilized for the source reconciliation. The aliphatic hydrocarbon and the biomarkers (triterpanes and steranes) distribution show a characteristic of the petrochemical source in the rainwater samples. The PAHs diagnostic ratios [e.g. MP/P, MPI, Fl/ (Fl + Py)] indicated vehicular emissions. The fatty acids ratios (e.g. C_18:1/C_18:0 and C_18:2/C_18:0) reflect the contribution of cooking emissions, while the higher plant waxes play little part. Moreover, the values of MP/P, MPI, BaA/(BaA + CT) and BeP/(BeP + BaP) reflected the origin of the long-distance transportation to some extent. On the whole, for the dry season rainwater, all molecular diagnostic ratios indicated the complexity of the organic composition of the rain, which have the characteristics of both a local emission contribution and a long-distance transportation contribution.     

Seasonal changes in microbial heterotrophic activity in subarctic marine waters as related to phytoplankton primary productivity

Water samples were collected in and near Kasitsna Bay (Cook Inlet), Alaska over 18 mo (February 1979–August 1980). Seasonal changes in glucose and glutamate uptake rates were measured in these samples. During the second year of the study, the uptake rates of glycolate and acetate and primary productivity were also measured. Of the substrates tested, significant positive linear correlations were observed between glucose and glutamate uptake and primary productivity. A higher correlation was observed between glucose to glutamate uptake ratios and primary productivity. The seasonal patterns of glucose uptake, glucose-to-glutamate uptake ratios and primary productivity rates show that the ratios changes simultaneously with fluctuations in primary productivity rates. The glucose uptake patterns reveal a delay in the response of the glucose-utilizing microorganisms to the onset of the bloom. It is suggested that by measuring the uptake rates of the simple compounds by microheterotrophs, and comparing these rates with each other, one can determine the relative flux of these compounds through the system. If the major source of these compounds is material released into the seawater by phytoplankton, it is possible that this approach could characterize the flux of extracellular products. As more is known about how the composition of extracellular material relates to the physiological state of phytoplankton, such an approach may eventually be a useful indirect assessment of the physiological state of natural phytoplankton populations.Published as Technical Paper No. 6397, Oregon Agricultural Experiment Station     

The effects of three oils on marine phytoplankton photosynthesis

The effects of 3 oils (Venezuelan crude, No. 2 fuel, and No. 6 fuel) on the photosynthesis of natural phytoplankton communities from Bedford Basin, Nova Scotia (Canada), and the northwest Atlantic Ocean between Halifax and Bermuda were examined using a radiocarbon method. The 3 oils can inhibit photosynthesis, and the degree of inhibition depends upon oil type and concentration. The No. 2 fuel oil was the most toxic. Under certain conditions, low concentrations of Venezuelan crude oil can stimulate photosynthesis. On the basis of these results, it is concluded that present levels of oil contamination in Bedford Basin could be inhibiting photosynthesis by a few percent, while present levels in open ocean water have no apparent deleterious effect on photosynthesis.Bedford Institute of Oceanography Contribution.     

南京市大气中挥发性有机物污染的研究

1　IntroductionVolatileorganiccompounds (VOCs)areimportantairpollutantsintheurbanatmosphere .SomeVOCsaretoxicandpotentiallycarcinogenic.ExposuretoVOCsisofconcernasitmayresultinsignificantrisktohumanhealth .AmbientVOCsareemittedfromvariousurban ,industrial…