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.     

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.     

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.     

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.     

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.     

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.     

自然风化条件下原油中金刚烷的风化规律

以渤海2个原油作为研究对象进行自然风化实验,探讨了原油中金刚烷化合物的分布情况及其风化规律.结果表明,经过100 d的室外自然风化,原油中金刚烷的分布已经发生了较大的改变：风化损失程度与金刚烷化合物的沸点有关,风化初期单金刚烷损失严重,风化45 d,单金刚烷完全消失;双金刚烷浓度变化较小,有较好的抗风化稳定性;通过t检验分析,所选取诊断比值中,单金刚烷指标A6、A8、A12和双金刚烷指标A16、A17、A18较为稳定,能很好地指示自然风化20 d内油样的来源;双金刚烷指标A17、A18风化100 d非常稳定,可用于长期自然风化油样来源鉴别,金刚烷化合物诊断比值对于溢油鉴别具有重要的意义.     

呼和浩特市冬季PM_(10)中多环芳烃的污染特征及来源解析

2013年12月在呼和浩特市主城区9个环境空气监测点位同步采集PM_(10)样品,对PM_(10)浓度和16种多环芳烃的浓度、污染特征进行了分析,使用特征比值和主成分分析对多环芳烃来源进行了解析.9个监测点位的PM_(10)浓度介于23.5—322μg·m-3之间,16种多环芳烃总量介于5.34—850 ng·m-3之间.荧蒽、芘、苯并[a]蒽、、苯并[b]荧蒽、苯并[a]芘、苯并[g,h,i]苝和茚并[1,2,3-cd]芘等多环芳烃单体浓度较高,这8种多环芳烃占多环芳烃总浓度的80.4%.主成分分析所获得污染源结果和特征比值法定性判断出的污染源结果一致,燃烧源、机动车尾气源和石油源为主要污染源,分别贡献61.3%、16.0%和10.4%.     

超声波萃取—GC／MS测定大气颗粒物中的多环芳烃

采用超声波萃取大气颗粒物样品中的多环芳烃，样品不须纯化，直接可用于GC／MS分析，超声波萃取效率高，萃取时间短；采用MS的SIM方式对多环芳烃进行定性定量，回收率84.5%-108.5%，变异系数3.1%-14.5%。     

北京市西北郊大气气溶胶中多环芳烃的源解析

用气相色谱-质谱技术对北京市西北郊2005-2006年大气气溶胶样品中的多环芳烃进行分析检测,并运用比值法、主成分分析/多元线性回归和正矩阵因子分解对多环芳烃的来源进行解析主成分分析/多元线性回归表明,机动车尾气、燃煤和生物质燃烧的贡献率分别为70.27%,21.84%和7.89%.正矩阵因子分解表明,汽油车的贡献较大,且各个季节都占优势;冬季燃煤的贡献增加,秋季生物质燃烧的贡献增大.多环芳烃的比值表明其主要来自于本地源.     

Short-term effect of microencapsulated hydrocarbons on shell growth of Mytilus edulis

Two North Sea crude oils, weathered crude oil, n-alkanes, medical liquid paraffin and a fish oil were microencapsulated and added to seawater. This gave a medium containing both water soluble fractions (WSF) and oil particles, and thus simulated the conditions in natural seawater contaminated with oil. The microencapsulated oils were fed to Mytilus edulis L. in different concentrations, and the growth in terms of shell length of the mussels was measured in intervals of 24 to 48 h for 4 to 12d. With the crude oilss A and B, weathered crude oil and n-alkanes at concentrations1 mg l^-1, shell growth rate decreased rapidly compared to controls. With liquid paraffin at levels of 1 to 12 mg l^-1, a small but significant negative effect on shell growth occurred after 5 d of exposure. Exposure to fish oil at 1 and 4 mg l^-1 gave no significant reduction in growth rate. The toxicity of the different hydrocarbons was not related to their content of aromatic fractions. Crude oil B was tested at concentrations ranging from 0.12 to 12 mg l^-1. At 0.12 mg l^-1 shell growth was not significantly different from the control, while at 0.25 and 0.50 mg l^-1 a temporary and significant stimulation of growth was observed. The product concentration (C)xresponse (R) shows a linear regression on exposure time (t). The regression model CxR=75-0.18t is used to estimate EC-values (effect of a given concentration) for given response levels. The model gives a very good fit to observed data.     

Encapsulation in cyclodextrins to widen the applications of essential oils

Environmental Chemistry Letters - There is a growing interest for aromatic and biological properties of essential oils as alternatives to synthetic chemicals and drugs. However, essential oils and...     

Chemical composition and effects of water extracts of petroleum on eggs of the sand dollar Melitta quinquiesperforata

Sperm and eggs of sand dollars, Melitta quinquiesperforata (Leske), were subjected to two petroleum oils, and effects determined. The oils chosen were Kuwait crude and No. 2 fuel oil, supplied by the American Petroleum Institute. Water-soluble extracts (WSF) from oil-sea water mixes were prepared and the major aromatic components in the WSF of the fuel oil were identified. WSF of No. 2 fuel oil depressed respiration, mobility of sperm, interfered with fertilization and cleavage, and retarded larval development. The effects were detectable at dilutions of 4% and less (about 0.6 ppm of WSF). Kuwait crude was much less toxic. There was no effect on water permeability of the egg membrane. Results are compared with similar studies on other marine organisms.     

Stimulation of soil microbial activity by essential oils

Summary. Although essential oils are well known antimicrobial agents, some microorganisms are activated by them and can use them as a carbon and energy source; this is the case for soil bacteria from Mediterranean ecosystems. We examined the assumption that soil microorganisms when offered with an essential oil, to which they had been previously exposed, would respond faster making immediate use of the newly added substrate. Origanum vulgare subsp. hirtum, Rosmarinus officinalis, Mentha spicata, and Coridothymus capitatus plants were collected and their essential oils isolated. Soil samples from the upper surface layer, beneath these aromatic plants, were also collected. All possible combinations of essential oils and soil samples were examined as well as the effect of the oil of R. officinalis and the non-indigenous, Lavandula angustifolia, on soil samples collected from cultivated fields. Soil respiration was used as a measure of the microbial activity. Oils (0.1 ml) were repeatedly added to the soil samples (150 g) and CO₂ release was measured every seven days. Essential oils differed in their chemical composition. In spite of that, they activated respiration of the different soil samples, even of those not previously exposed to essential oils, to a comparable degree. These results suggest that essential oils are used as a carbon and energy source by rather ubiquitously occurring soil microorganisms and provide evidence that they would not accumulate in the soil, if environmental conditions favour growth of these microorganisms.     

Polycyclic aromatic hydrocarbons in Syrian olive oils and their likely daily intakes

The levels of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (16 EPA PAHs) in Syrian olive oils have been determined. Forty-two samples including commercial extra virgin and virgin olive oils, and virgin olive oils from olive mills were analyzed. Only naphthalene (NAP) was detected in all olive oil samples under investigation. Among the studied 16 EPA PAHs, the highest maximum concentration was also observed for NAP (120 μg kg^?1). Moreover, three samples exceeded the European Union (EU) maximum level of 2 μg kg^?1 for benzo[a]pyrene (BaP) in oils and fats, and only one sample exceeded the EU maximum level of 10 μg kg^?1 for the sum of benz[a]anthracene, chrysene, BaP, and benzo[b]fluoranthene (PAH4). The likely daily intakes of the total sum of 16 EPA PAHs, the sum of eight genotoxic PAHs, the sum of PAH4, the BaP, and the BaP equivalent through consumption of Syrian olive oils were estimated.     

Individual and combined toxicity of some petroleum aromatics to the marine amphipod Elasmopus pectenicrus

Toxicity of 4 components of petroleum oils to the marine amphipod Elasmopus pectenicrus (Bate) has been assessed. Two ephemeral aromatic hydrocarbons, naphthalene (A) and 1, 2, 4-trimethylbenzene (B) were more toxic than two persistent aromatics, o-cresol (C) and o-toluidine (D). The acute toxicity concentrations obtained for individual aromatic compounds were always greater than the actual concentrations found in the water-soluble fractions (WSF) of fuel oils. Results from mixtures of 2 or more components indicated that the LC₅₀ levels were primarily determined by the more toxic substances, A and B. Naphthalene and 1, 2, 4-trimethylbenzene became more toxic to the E. pectenicrus when present in a mixture of more than 2 components, and the toxicity increased with increasing numbers of components present. Synergistic effects, therefore, possibly occur in the whole WSF. No antagonistic effects were observed among the 4 petroleum aromatics.University of Texas, Marine Science Institute Contribution No. 290     

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.     

Abundance and diversity of the phyllosphere bacterial communities of Mediterranean perennial plants that differ in leaf chemistry

Summary.  We studied the epiphytic bacterial communities of the summer leaves of eight perennial species naturally occurring in a Mediterranean ecosystem. The species differ in essential-oil content (from rich in essential oil to non-producers) and composition, and also in life form (from herbaceous species to tall shrubs). We compared the epiphytic bacterial communities on the basis of (i) their abundance, (ii) their metabolic profile (derived by use of the BIOLOG Ecoplate system) and (iii) richness and diversity of substrates that they use, as a measure of functional diversity. Among all species, the aromatic Melissa officinalis was the most abundantly colonized. The bacterial communities on the leaves of the aromatic Myrtus communis, Calamintha nepeta and Melissa officinalis, and also of Cistus incanus catabolized all 31 substrates offered; those on the evergreen-sclerophyllous species, Arbutus unedo and Quercus coccifera, catabolized only 14 and 17 substrates, respectively. Carbohydrates were consistently used abundantly by all communities, whereas carboxylic acids were most variably used. On average, the group of aromatic plants scored higher regarding bacterial abundance, and richness and diversity of substrates used by the bacterial communities on their leaves; the lowest values for both substrate-use indices were recorded in A. unedo. Bacterial abundance or richness or diversity of substrates used did not vary with leaf oil content. Abundance was positively correlated with both substrate-use indices. Results support claims that the antimicrobial effects of essential oils are not exerted so much under natural conditions as reports based on biassays with pathogens usually show. Although essential oils play a part in the microbial colonization of the phyllosphere, it is not likely that inhibition of phyllosphere bacteria is essential oils’ primary role, at least in the Mediterranean environment.     

QSAR法研究芳烃类化合物的生物毒性

基于表征生物活性的原子点价Bi并构建芳烃类化合物的拓扑指数Ln,并用L0,L1及指示参数N与芳烃类化合物对发光菌、大型蚤、呆鲦鱼的急性毒性关联,得到了良好的相关性,相关系数依次为0.9489、0.9787、0.9648,所建QSAR模型具有良好的稳定性和预测能力,估算结果均明显优于文献方法。     

Occurrence of tar balls on the beaches of Fernando de Noronha Island,South Equatorial Atlantic

This work reports on the widespread occurrence of tar balls on a pebble beach of Sueste Bay on Fernando de Noronha Island, a Brazilian national marine park and a preserve in the South Equatorial Atlantic. Environmental regulations preclude regular visitors to the Sueste Bay beach, and the bay is a pristine area without any possible or potential sources of petroleum in the coastal zone. In this work, these tar balls were observed for the first time as they occurred as envelopes around beach pebbles. They are black in color, very hard, have a shell and coral fragment armor, and range in average size from 2 to 6 cm. The shape of the majority of the tar balls is spherical, but some can also be flattened ellipsoids. The polycyclic aromatic hydrocarbon analyses of the collected samples revealed the characteristics of a strongly weathered material, where only the most persistent compounds were detected: chrysene, benzo(b,k)fluoranthene, dibenzo(a,h)antracene and benzo(a)pyrene.