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.     

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.     

船舶燃料油中主要多环芳烃的短期风化特性

本文通过特制的溢油风化模拟装置对船舶燃料油进行了风化实验,采用气-质联用仪(GC-MS)对风化样品中的多环芳烃进行了检测,通过谱图和特征分析,研究了船舶燃料油中主要多环芳烃的风化规律.结果表明:船舶燃料油中主要多环芳烃组分含量由高到低依次为萘类>菲类>二苯并噻吩类>芴类> 类,在每类同系物中,带支链的同系物含量基本上高于未带支链的多环芳烃母体;风化时问明显影响着船舶燃料油中多环芳烃组分的相对含量,在5组多环芳烃中,萘系列组分风化速度最快,其次为芴系列组分,菲、二苯并噻吩和系列三组分不易风化;风化1周内,船舶燃料油中多环芳烃同分异构体C1D(m/z=198)和C1P(m/z=192)与特征参数比值C22D/C2P、C2D/C2、∑P/(∑D+∑P)基本保持稳定.风化2周内,多环芳烃同分异构体C1D(m/z=198)与C1P(m/z=192)中分布相对靠前的组分更易风化,特征参数比值C2D/C2P明显下降,C3D/C3P与∑P/(∑D+∑P)仍然保持稳定.     

渤海中部油气开采区石油烃环境质量评价及源解析

对渤海中部油气开采区表层沉积物中的石油烃含量进行了环境质量评价,分析了正构烷烃和多环芳烃分子组成特征,并对其来源进行了解析.结果表明,石油类浓度为12.5—860μg·g~(-1)之间,污染指数为0.61—41.97;随着与采油平台距离的增加,平台周边海域石油烃含量和污染水平呈现降低的趋势;沉积物沉积时为缺氧还原的沉积环境.正构烷烃的分布特征和甾萜烷生物标志化合物表明,源自大陆高等植物和海洋浮游生物的烷烃共存于渤海近代沉积物中,石油类产品和化石燃料燃烧产物对其贡献不能忽视;石油平台站位PAHs主要来自石油的直接输入,其它站位主要来自燃烧源.     

全二维气相色谱-飞行时间质谱(GC×GC/TOFMS)对比研究不同燃料油中烷烃和芳烃的图谱特征

采用全二维气相色谱-飞行时间质谱(GC×GC-TOFMS)方法对比研究不同沸程燃料油(93号和97号汽油、0号柴油和重柴油)中烃类组分的全二维谱图特征,经过对色谱和质谱条件的优化,较好地实现了不同汽油和柴油中烷烃、规则类异戊二烯烃、十氢化萘系、四氢化萘系、萘系、菲系等族组分分离和目标化合物分离,各族化合物均呈现显著的"瓦片效应"的特征.4类燃料油的烃类碳骨架分布、正构烷烃与姥鲛烷和植烷的比值以及不同族化合物的相对丰度等存在较显著的差异.     

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.     

渔业养殖区藻源溶解性有机质性质特征对汞甲基化影响

溶解性有机质(dissolved organic matter,DOM)是水生生态系统中的重要成分,能够显著影响汞的甲基化等形态变化过程.以近岸渔业养殖区藻源DOM为研究对象,运用傅里叶变换红外光谱和三维荧光光谱技术,对其结构特征进行表征;并选取总有机碳浓度TOC_DOM=10 mg·L^-1(DOM₁₀)和TOC_DOM=50 mg·L^-1(DOM₅₀)两种水平藻源DOM提取液,分析其在不同汞浓度条件下对汞甲基化过程的影响.结果表明,藻源DOM主要由类蛋白和类腐殖质组分组成,其中前者含量较高,疏水及芳香组分含量较低;红外光谱显示藻源DOM中含有—OH、—CH₃、—CH₂、芳香性C=C等官能团.甲基化实验表明,在溶液中DOM含量相对较少时(DOM:Hg浓度比≤15625),DOM表现出抑制汞甲基化的趋势,而当溶液中DOM含量逐渐升高(DOM:Hg浓度比>15625),DOM可以显著促进水体中汞向甲基汞的转化.藻源...     

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.     

丹江口水库表层沉积物有色可溶性有机物空间分布特征及其来源分析

利用三维荧光光谱(Excitation-emission matrices,EEMs)与平行因子分析模型(Parallel factor analysis,PARAFAC)技术研究丹江口水库表层沉积物有色可溶性有机物(Chromophoric dissolved organic matter,CDOM)荧光组分、空间分布特征和来源,以及不同组分荧光强度与其它沉积物指标的相关性.结果表明,丹江口水库37个采样点CDOM由3类5个荧光组分组成,即类蛋白组分C1(285/345 nm)和C2(225,270/335 nm);陆源类腐殖质组分C3(260/450 nm)和C4(360/450 nm)及自生源类腐殖质组分C5(225,310/405 nm).其中代表类蛋白组分的C1和C2占较高比例,占总荧光强度的百分比的平均值为46.37%,C3与C4和C5占总组分的比例平均值分别为34.33%和19.31%.空间分布上3种荧光峰高值都集中在汉江的入湖河口处及丹江库区居民较多的城镇处,且呈现河流大于库区的趋势.荧光指数(FI)、腐殖化指数(HIX)和生物源指数(BIX)都表明丹江口水库沉积物CDOM的来源具有陆源及生物源的双重特征,陆源主要来源于汉江干流和周边城市居民的活动,以及部分区域农业畜禽养殖;生物源主要来自微生物及藻类的降解.相关性分析说明沉积物CDOM与N、P元素的迁移和转化有密切的关系.     

东平湖可溶性有机物的荧光特征及环境意义

东平湖作为南水北调东线工程最后一级调水湖泊以及山东省西水东送的水源地,其水质状况对受水区的用水安全起决定性作用。基于2013年8月的东平湖采样,对各水质参数分析发现,东平湖目前仍处于中富—富营养化水平,水质总体接近GB 3838—2002《地表水环境质量标准》IV类水质标准,仍不能满足调水要求,各水质参数表现出强烈的外源性。利用三维荧光光谱(EEMs)并结合平行因子分析法(PARAFAC)解析东平湖有色可溶性有机物的荧光特征,并探讨了荧光组分对东平湖环境污染指示意义的可行性。利用平行因子分析法(PARAFAC)共识别出2类4个荧光组分,分别是类腐殖质荧光组分C1(225/305,386 nm)、C3(260,432 nm)和类蛋白荧光组分C2(240,360 nm)、C4(225/275,304 nm)。相关性分析发现,陆源类腐殖质荧光组分C1与间接反映有机污染程度的溶解性有机碳(DOC)和化学耗氧量(COD)具有显著相关性,类蛋白荧光组分C2与总氮具有显著正相关性,可以对东平湖富营养变化情况进行快速、长期的监测。     

西南部分地区麻疯树种子油的理化性质及脂肪酸组成分析

从西南6个地区采集了麻疯树种子并分析比较了其生物学性状和种子油的理化性质及脂肪酸组成.所有样品的百粒重范围为41.80~71.39g,出仁率60.02%~81.43%,种仁含油率51.76%~57.93%,种子含油率31.07%~47.17%,不饱和脂肪酸含量74.89%~79.68%.其中永胜产麻疯树的种子品质最好,其出仁率为81.43%,种仁含油率57.93%,种子含油率47.17%,不饱和脂肪酸含量79.68%.攀枝花和宁南产麻疯树的种子品质次之.双柏和罗甸麻疯树的种子油酸值为0.81,在所有样品(0.81~9.46)中最低.对麻疯树种子及种子油性质的相关数据进行方差分析,结果表明,产地不同,麻疯树种子的生物学性质、种子油理化性质和脂肪酸组成都有一些差异.图2表3参18     

Origin,occurrence, and biodegradation of long-side-chain alkyl compounds in the environment: a review

Long-side-chain alkyl compounds, such as those present in oil and oil products, either of natural or of anthropogenic origin or released by industrial activities, are a ubiquitous group of chemicals in the environment. Among them, long-side-chain alkylmonocycloalkanes, alkylbenzenes, and alkyl organic sulfur compounds are largely found in fossil fuels while long-side-chain alkylbenzene sulfonates and alkylphenols are released into the environment primarily due to domestic activities. The present article briefly summarizes the advances that have occurred in this field in terms of the identity, abundance, possible origin and significance of these long-side-chain alkyl compounds found in the environment. In addition, the susceptibility to biodegradation and the fate of these chemicals in the environment are discussed.     

Recovery of benthic communities at Macquarie Island (sub-Antarctic) following a small oil spill

Intertidal communities at Macquarie Island (sub-Antarctic) were re-evaluated seven years after a small oil spill resulting from the grounding of the “Nella Dan”, and six years after the first assessment of biological impact. Sampling was conducted to evaluate community structure in three zones of the exposed rocky shore (upper red, kelp, and lower red) and in samples of Durvillaea antarctica holdfasts. There were no significant differences between the community structure in oiled and control locations in any of the three shore zones, but holdfast macrofaunal communities at oiled sites still showed evidence of impact. Holdfast community-structure in samples from heavily oiled sites showed moderate levels of recovery, with increased abundances of species which were considered sensitive to the oiling in the first post-impact studies and decreased abundances of opportunistic polychaete and oligochaete worms. In contrast, samples collected from the moderately oiled location at Secluded Bay showed little evidence of recovery. Holdfasts at this site were filled with sediment containing traces of diesel oil, and the macrofaunal community was dominated by opportunistic worms. This study clearly indicates that even small incidents of anthropogenic perturbation can have long-lasting consequences for marine communities at Macquarie Island. Received: 23 July 1997 / Accepted: 5 February 1998     

牡丹皮、川芎和石菖蒲挥发油提取工艺研究

目的确定牡丹皮、川芎和石菖蒲挥发油最适宜的提取工艺方法．方法用共水回流冷凝法研究了三种药材混合提取及分开提取挥发油的工艺方法,以挥发油的重量为指标来评价提取工艺．结果混合提取及分开提取所获得的挥发油的重量,经统计学分析无显著性差异（P〉0．05）．结论共水回流冷凝法混合提取牡丹皮、川芎和石菖蒲挥发油的工艺可行、简便,适合工业化大生产．表5,参3     

Alkyl polyglucosides as cell surface modification factors: influence of the alkyl chain length

The use of surfactants in a bioremediation process is aimed at increasing the efficiency of the removal of hydrophobic contaminants from the environment. The subjects of the study were three alkyl polyglucosides (APGs) of different alkyl chain length: Glucopon 215 CS UP, Glucopon 600 CS UP, and Glucopon 650 EC. The impact of these surfactants on the surface properties of the test strain Pseudomonas fluorescens ATCC 14700, as well as on the biodegradation of diesel was tested. It was observed, that the length of alkyl chain has an influence on the cell surface properties. The modification of the cell surface hydrophobicity and the electrokinetic potential on the bacteria cells is dependent on the structure of Glucopon molecules. The elongation of alkyl chains in surfactant molecule caused an increase of the hydrophobic properties and a reduction of the electrokinetic potential on the bacteria cells. Moreover, the use of APGs below critical micelle concentration caused an increase of diesel oil biodegradation, especially in the case of Glucopons with longer alkyl chain (Glucopon 600 CS UP and 650 EC). The better diesel oil removal by tested strain after surfactant addition was correlated with the hydrophobic properties of bacteria strain.     

油藏微生物群落分布及提高采收率的模拟实验研究

对取自大庆油田各类油藏的126个地层油水样品中部分微生物进行了培养计数和分析,检测出大庆油田地层水中含有好氧和厌氧微生物9类.在此基础上,进行了微生物提高石油采收率的物理模拟试验.结果表明,通过激活油藏地层水中的微生物,可以使油藏压力上升0.2MPa,并提高采收率幅度9%以上.     

Do artificial structures alter marine invertebrate genetic makeup?

Human-made structures are increasingly built in marine coastal habitats for a variety of purposes. Offshore oil and gas production platforms are among the largest examples. Yet, biological effects of these increasing density artificial substrata are under evaluated. The objective of our study is to investigate the possible role of offshore platforms in modifying the genetic composition of populations of natural rocky shores species. The serpulid Pomatoceros triqueter was used as a model, and genetic variation was assessed using a 419?bp fragment of the mtDNA COI gene in samples collected on eleven offshore gas platforms, on one coastal buoy on the sandy shore and in four sites located on natural rocky shores in the Adriatic Sea. Deep phylogenetic lineages were uncovered over all samples. Nucleotide diversity and mean number of pairwise differences among haplotypes were significantly smaller in offshore platform samples compared to rocky shores samples. No significant genetic structure was observed over all samples. We found direct evidence of lower genetic diversity on platforms confirming that, although artificial structures attract and support species typical of hard bottoms, they are not analogues of natural rocky habitats.     

Nocturnal changes in the mean length of a euphausiid population: vertical migration,net avoidance,or experimental error?

The lengths of 9 421 Antarctic krill, Euphausia superba Dana, from 144 net samples from 4 depth ranges at the same location (north east of South Georgia) were measured over a period of 6 d. While the mean lengths showed differences between each depth range in each time period of each day, the only consistent difference occurred in the period 00.00 to 04.00 hrs local time, when the mean lengths of krill were up to 2 mm greater than those found at other times. While vertical migration may have contributed to this nocturnal change in mean length, differences in measurement techniques between observers were also implicated. Controlled laboratory experiments confirmed that there were significant differences between measurements of the same krill analysed by six different observers while there were no significant differences in replicate measurements made by a single observer. These results have important implications for future studies involving length and length-frequency analysis, and suitable precautions and experimental protocols are suggested.     

Possible Use of Rna:Dna Ratio for Detecting Oil Induced Disturbance: A Field Report

The effects of oil contamination on the metabolic state of suspended participate and sedimented organic matter were investigated through the analysis of the RNA:DNA ratio on samples collected from January 1991 to January 1992 in the Ligurian Sea (northwestern Mediterranean). the ratio of RNA to DNA appeared to be highly sensitive to hydrocarbon stress since the oil disturbance resulted in an evident decline in the RNA:DNA ratio relative to the pre-pollution conditions. Such a pattern was unusual since it occurred in a period when we would expect a seasonal increase in bacterial activity. Differences are seen when comparing the temporal trend of DNA in suspended particulates and in sediments. However, the effects of oil on the RNA:DNA ratio were similar. Oiled samples showed a RNA:DNA ratio lower than 1 whereas RNA concentrations exceeded DNA content in undisturbed samples. Bacterial DNA accounted for a significant fraction (average 26%) of total DNA in sediments. It is likely that changes in RNA:DNA ratio in oiled sediments are due to the disturbance of bacterial communities. Consistent with the meiofaunal response to oil contamination, the hydrocarbons had only temporary and limited effects and RNA:DNA values recovered to pre-pollution conditions after a few weeks. the possible use of the RNA:DNA ratio in pollution monitoring is discussed.     

滨海城市不同粒径大气颗粒物中水溶性离子的分布特征

选取东南滨海城市厦门的城区（厦门大学,仙岳小区）、郊区（集美大学城）、工业区（鹭联宾馆）和背景区（汀溪水库）5个站点为研究对象,于2008年10月至2009年9月对厦门市大气PM2.5、PM2.5-10和PM10-100分4个季节进行了采集工作,用离子色谱对其中的水溶性离子进行测定。研究结果表明,厦门市不同粒径颗粒物中水溶性离子具有明显的时空分布特征,且主要以富集在细颗粒物（PM2.5）上为主。SO42-、NO3-和NH4＋是PM2.5中主要的水溶性离子,占PM2.5中水溶性离子总质量浓度的64.59%～93.17%。PM2.5-10和PM10-100的水溶性离子则以Na＋、C1-和Ca2＋这些粒径较大的颗粒为主。滨海城市厦门PM2.5、PM10和TSP的SO2转化率（SOR）和NO2的转化率（NOR）年平均值分别为：0.35、0.39、0.41和0.04、0.08、0.09,较高的SOR和相对较低的NOR比值均说明厦门存在来自于SO2和NO2转化的二次污染物SO42-和NO3-。