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.     

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.     

胶州湾南部溢油海域表层沉积物油指纹特征参数变化

2013年11月22日青岛黄潍输油管道发生了泄漏爆炸事故,为研究溢油在真实海洋环境中的风化过程提供了可能.本文以2015—2017年青岛胶州湾南部近岸海域的4次调查沉积物样品为对象,采用GC/MS等分析手段,研究了溢油海域表层沉积物中生物标志物的分布特征和特征比值的波动规律,分析了沉积物有机质影响的可能来源.结果表明,溢油海域表层沉积物各站位不同碳数的三环萜烷类和不同立体构型的藿烷类,胆甾烷、甲基胆甾烷和乙基胆甾烷均有检出,Ts/Tm比值较低,可能与生物降解作用有关,比值C31αβ(S/(S+R))、C29甾ααα(S/(S+R))均接近于0.6,指示该区域受到石油输入的影响;溢油海域沉积物各站位甾烷、萜烷特征参数比值分布模式基本一致,表明调查海域有机质组成具有一致性,甾烷、萜烷类特征参数比值随着时间的变化呈现不同规律性的变化,表明溢油污染的海域沉积物受石油污染控制已经较弱,主要受海洋环境有机质输入等自然因素的影响.调查海域沉积物甾烷类物质主要来源于高等植物、浮游生物和藻类共同输入的混源有机质.     

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.     

基于发光细菌法和鱼类暴露实验评价6种化学消油剂的遗传毒性

为评价海洋溢油应急处置中所使用的消油剂的环境安全性,分别以发光细菌Acinetobacter sp.Rec A和海水青鳉(Oryzias melastigma)幼鱼为受试生物,对6种化学消油剂的遗传毒性进行检测.结果显示,采用发光细菌法仅检测到HLD-501(常规型)在浓度较高(500 mg/L和1 000 mg/L)时表现出一定水平的遗传毒性,其等效应的丝裂霉素C(MMC)浓度分别为0.039 mg/L和0.032 mg/L.在彗星实验中,6种消油剂对海水青鳉幼鱼细胞的DNA损伤率从高到低依次为RS-II(浓缩型)、RS-I(浓缩型)、HLD-501(常规型)、富肯-2(常规型)、RS-I(常规型)和微普(常规型),然而HLD-501(常规型)处理的3级损伤率最高,其遗传毒性最大.综上,采用两种不同营养级的受试生物对6种化学消油剂遗传毒性检测结果的相关度较好;本研究可为消油剂用于处理实际海洋溢油污染的环境安全性评价提供参考.     

消油剂与120#燃料油对马粪海胆(Hemicentrotus pul-cherrimus)抗氧化酶活性的影响

在溢油事故应急处置中,消油剂的使用备受争议。为探究消油剂和溢油对海洋底栖模式生物海胆(Hemicentrotus pulcherrimus)复合毒性效应,通过WAFs(Water-accommodated fractions)和CEWAFs(Chemically enhanced water-accommodated fractions)的96 h暴露实验,测定海胆肠和性腺中过氧化氢酶(CAT)、超氧化物歧化酶(SOD)、谷胱甘肽硫转移酶(GST)、谷胱甘肽过氧化物酶(GPx)活性的变化。实验结果表明:随油水配比浓度的增加,4种酶活性呈现先升高后降低趋势,且酶活性峰值均极显著高于海水对照组水平(P0.01)。肠中4种酶活性最大诱导倍数均高于性腺。相同暴露浓度下,CEWAFs组4种酶活性诱导程度均高于WAFs组。消油剂对照组和海水对照组间4种酶活性则无显著性差异(P0.05)。     

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.     

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.     

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.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

A graphical assessment and spatial clustering of the Deepwater Horizon oil spill impact on Laughing Gulls

The Deepwater Horizon oil spill occurred in the Gulf of Mexico on April 20, 2010. Considered the largest accidental marine oil spill in history, oil flowed for three months and approximately five million barrels of oil spilled through by mid-July 2010. In this article, we analyze bird data to assess the impact of the oil spill on the Gulf wildlife. Particularly, we want to determine in which regions Laughing Gulls were mostly affected by the oil spill, and whether those regions spatially shifted throughout the year 2010. Though our data sets have some limitations to apply statistical analysis methods, we obtained very interesting results. Our analyses showed the general consistency of the results based on two population data sets (from the 2011 Data Expo and from the eBird community) and justified the use of both publicly available data sets. We showed that the closer the surface oil spill area approached to the Laughing Gulls habitats, the more significant clusters of bird cases were observed.     

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.     

海洋溢油污染的生态与健康危害

随着溢油事故的频繁发生,海洋溢油污染备受关注.本文在阐述国内外海洋溢油污染现状的基础上,针对溢油污染对人类健康的影响进行了初步分析,并针对海洋环境中溢油的环境行为以及对海洋生态系统、沿岸滩涂生态系统的毒性效应进行了概述.最后,对海洋溢油污染研究的发展趋势进行了展望.     

溢油分散剂中吐温80对石油中多环芳烃在海水中光降解的影响

溢油事故发生后喷洒溢油分散剂是常用的应急措施之一,这使得溢油分散剂中的表面活性剂与石油中的重要污染物多环芳烃(PAHs)在海水中共存。光化学转化是水中PAHs的重要转化途径,这些共存表面活性剂如何影响PAHs在海水中的光化学消减还有待阐明。本研究选取溢油分散剂的重要活性成分吐温80和石油中2种不同类型的PAHs(菲和二苯并噻吩),通过光化学实验考察不同浓度吐温80对菲(PHE)和二苯并噻吩(DBT)在海水中的光降解速率常数和光解量子产率的影响,并通过量子化学计算的手段研究其影响机制。研究发现:吐温80可以使PHE和DBT的阳离子自由基回到稳定的基态,降低PHE和DBT的光解量子产率,从而抑制PHE和DBT的光降解。该结果表明,在评价溢油分散剂的风险性时不可忽视其对PAHs环境转化行为的影响。     

Mid-depth oil concentration due to vertical oil dispersion in a regular wave field

An experimental program is organized to investigate the vertical oil dispersion of surface oil spills in a regular wave field. Various waves characteristics and different volumes of oil spills are tested to assess the oil concentration variations at two sampling stations. It is found that the oil concentration due to vertical oil dispersion follows an ascending diagram to reach a maximum and then decreases while oil slick passes the location. The maximum mid-depth oil concentration (C_max) at the farther sampling station is 30–50 % less than the concentration at the closer sampling station to the spill location. A 50 % increase in oil spill volume causes 30–60 % growth in oil concentrations. The relations between oil concentration and important parameters such as wave characteristics, amount of spilled oil and the distance of sampling stations from the spill location are indicated and also oil concentration variations are quantified. Two equations are derived through statistical analysis of the obtained experimental data, which estimate the magnitude and time of maximum oil concentration.     

Environmental disaster,pollution and infant health: Evidence from the Deepwater Horizon oil spill

In 2010 the Gulf Coast experienced the largest oil spill affecting U.S. waters in history. Evaporating crude oil and dispersant chemicals can cause major health problems. This paper examines the impact of the Deepwater Horizon oil spill on air quality and infant health outcomes. Using U.S. Environmental Protection Agency (EPA) AirData, vital statistics data from National Center for Health Statistics (NCHS), and a difference-in-difference methodology, we find that the oil spill of 2010 increased concentrations of PM2.5, NO2, SO2, and CO in affected coastal counties, increased incidence of low birth weight (<2500 g) and premature born infants (<37 weeks of gestation). Heterogeneity effects reveal more pronounced adverse infant health outcomes for black, Hispanic, less educated, unmarried, and younger mothers. Results are robust to a wide range of controls and robustness checks.     

Effect of microbial seeding of crude oil in seawater in a model system

The adding of a mixed culture of marine hydrocarbon-degrading bacteria to petroleum polluted seawater did not increase the hydrocarbon degradation capability of the water. All the strains of the mixed culture disappeared from the dominant microflora while the autochthonous bacteria showed a capacity for adaptation to petroleum degradation about four days after the oil spill. This confirms the advantage of natural bacterial communities. The oil spilled on the sea surface evolved very quickly under the influence of abiotic factors such as sunlight. Aromatic petroleum fractions were oxidized and polymerized. This chemical evolution causes a drastic decrease of the biodegradability of crude oil.