综合风化条件下渤海原油中PAHs 变化特征研究

以渤海某原油作为研究对象进行50 d综合模拟风化实验,探讨了原油中五类PAHs组分的分布情况及其风化规律.结果表明:经过50 d风化,原油中PAHs的分布发生了较大的改变:萘系列化合物损失最为严重,相对浓度的损失达到56.78%;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,其分布特征变化规律为进一步筛选溢油来源鉴别新诊断比值参数提供了一定的导向性;经风化检验,现有常用6种PAHs诊断比值在风化50 d后稳定性良好,可用于风化溢油的鉴别.     

The long-term effects of crude oil on microbial processes in subarctic marine sediments

Subarctic marine sediments were exposed to fresh and ‘weathered’ crude oil from Cook Inlet, Alaska. The crude oil was thoroughly mixed with the sediment at various concentrations and some of the oil-sediment mixtures were placed on top of unamended sediments. Both sediments with added oil and those overlain by oiled sediments were investigated. These sediments were placed either in trays or aquaria. The trays were incubated in situ near the site from which the sediments were originally collected. The aquaria were maintained at simulated in situ conditions by maintaining a continuous flow of fresh seawater through them. The sediments were exposed to crude oil for periods up to 1.5 years. Sediments exposed to 50‰ fresh crude oil showed significant decreases in nitrogen fixation and denitrification rates and redox potentials. Also observed were increases in CO₂ production rates and methane concentrations. These same changes were observed in sediments exposed to 1‰. When ‘weathered’ crude oil was added to the sediments, the same changes were observed except there was no reduction in nitrogen fixation activity. In most cases, the observed effects were less marked when the sediments were amended with ‘weathered’ crude oil than with the same concentration of fresh crude oil. Untreated sediments that were overlain with treated sediments showed the same changes as those sediments that were thoroughly mixed with crude oil. The presence of fresh crude oil at 50‰ essentially eliminated burrowing activity of the benthic infauna. Under these conditions, there was an accumulation of detritus particles on the oiled sediments that was not present in the untreated controls.     

Normal paraffin profiles of pelagic tar samples from the marmap survey

Pelagic tar samples from twenty stations on cruises of the research vessels ALBATROSS IV (72-6) and DELAWARE II (72-19) were analyzed by gas chromatography to obtain semi-quantitative profiles of normal paraffins in the range from C₁₀ to C₃₅ and a qualitative indication of the relative amount of other compounds having a volatility in that same range. These samples are essentially all weathered residues of waxy paraffinic crude oils, and are similar (with respect to the parameters measured) to numerous samples collected in the Sargasso Sea near Bermuda.     

多环芳烃油指纹应用于船舶溢油鉴别研究

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。     

气相色谱用于渤海采油平台原油的鉴别

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.     

Impact of crude oil on sulphate reduction and methane production in sediments impacted by the Amoco Cadiz oil spill

The activities of methane-producing and sulphate-reducing bacteria in intertidal sediments along the Brittany coast of France were examined in order to determine the effect of the Amoco Cadiz oil spill on sediment microbial processes. Porewater chemistry, methane production, sulphate rate and [2?¹⁴C]-acetate metabolism did not vary significantly between beach, estuary, and marsh sites, oiled or unoiled, after the Amoco Cadiz spill. Oiled sediments contained highly weathered oil of Amoco Cadiz origin, but unoiled comparison sites also contained hydrocarbons from anthropogenic sources. The additions of weathered Amoco Cadiz mousse, fresh and slightly weathered light Arabian crude oil, benzene or toluene to sediments from the oiled and unoiled marsh site did not significantly affect rates of sulphate reduction or methane production. The oxidation of [2?^14C]-acetate to ¹⁴CO₂, however, was significantly decreased when mousse, crude oil, benzene or toluene was added to sediments from the unoiled site. Inhibition seemed to be proportional to the extent of weathering. Sediments recently exposed to Amoco Cadiz crude oil were less affected by a second oiling, suggesting that the indigenous populations may have been replaced by organisms more resistant to oil toxicity. These results suggested that the Amoco Cadiz oil spill did not have major long-term effects on sulphate reduction or methane production.     

基于五种油源的中重度风化溢油的常规鉴定指标的应用效果评估

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。     

Effects of crude oil on the supralittoral meiofauna of a sandy beach

The supralittoral zone of an open sandy beach was dosed with crude oil and changes in the meiofauna monitored. Treatments included weathered and fresh oil on the surface, fresh oil mixed with dispersant on the surface and weathered oil at the water table, all in layers 0·8 cm thick. In all cases the meiofauna was reduced 1 month after dosing but numbers had returned to normal by 5 months except in the site dosed with fresh oil mixed with dispersant. Oil on the surface had greater effects than oil at the water table; fresh oil had a greater effect than weathered oil and fresh oil with dispersant was more toxic than fresh oil alone. Nematodes were least sensitive to the oil and oligochaetes more sensitive, their numbers being correlated with oil concentrations and depth in the substrate. It is concluded that, under all but the heaviest conditions of pollution in their environment, recovery from oil contamination should occur within 5 months in the meiofauna.     

渤海原油的蒸发风化对油指纹的影响

选取渤海3个不同区块不同平台的原油样品,进行室内蒸发风化模拟实验.采用气相色谱法和气相色谱一质谱联用法,分析了在不同风化程度(最大风化、最大风化的1/3、最大风化的2/3)下正构烷烃、生物标志化合物以及用于溢油鉴别的诊断比值在风化过程中的变化特征,探讨了渤海不同原油的蒸发变化过程,对渤海溢油鉴定具有重要的借鉴作用.     

短期风化对混合溢油组成的影响

对两种原油进行混合配比实验,将混合后油样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,短期风化作用对混合溢油的油指纹、生物标志化合物诊断指标等的影响。结果表明,混合溢油的正构烷烃总质量变化与单一原油油品的变化规律相近,即前期风化较快,质量减损较多,而后期风化趋缓,不同混合比例的溢油表现差异不明显。常用于短期风化的诊断比值对各混合油样的风化具有指示意义,但难以定性鉴别油品是否发生混合。重复性限法检验只能判定短期风化过程前后的油样为同一油源,而难以反映油样是否为混合油源的特征,各诊断比值的RSD%值较大可能是混合溢油的一个表现。     

原油中的正构烷烃类在海沙和海水中风化的模拟实验

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%.     

Oil pollution in the Izu Islands waters

The oil pollution in the Izu Islands waters are observed as follows:

1. Globules and lumps of oil were collected 2.56 g on the average in wet weight by each taw(174 m³) of a larval net at 389 stations, up to the maximum collection of more than 500 g.
2. On the investigation of the Oshima—Torishima line (J1–J10), globules and lumps of oil were collected more at the south of the Kuroshio Current than at the north.
3. In the coastal region (T1–T19) of Japan, many globules and lumps of oil were collected when a cold water mass was located at the west side of the Izu Islands, from south to east side of where the Kuroshio Current took a roundabout and closed near to the Bōsō peninsula (Aug. 1971, Jun. 1972, Aug. 1972), or when the Kuroshio Current took a roundabout the cold water mass which extended as far as Oshima from the coast of the Bōsō peninsula (Sept. 1971).

     

Changes in the volatile hydrocarbon content of Prudhoe Bay Crude Oil treated under different simulated weathering conditions

Changes have been determined in the concentrations of volatile saturate and aromatic hydrocarbons in Prudhoe Bay Crude Oil (PBC) weathered under three different simulated environmental conditions. A combination of light and water sprayed upon the surface of the oil produced the largest relative decreases in volatile saturate and most aromatic hydrocarbons. After 24 days, detectable amounts of monoaromatic hydrocarbons were absent in all three weathered oils, as were the saturate hydrocarbons from C₈ to C₁₀. Retention of aromatic hydrocarbons appeared to be related to molecular weight, as enrichments of triaromatics (phenanthrenes) were observed in weathered PBC relative to the original crude oil. These data are discussed with respect to effects resulting from spilled oil impacting benthic organisms residing in intertidal and shallow subtidal communities.     

混合原油的甾萜类和多环芳烃标志物短期风化规律研究

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。     

正构烷烃气相色谱指纹法鉴别海面溢油源一事例研究

通过对厦门海域一个具体海面溢油事例的研究，探讨了鉴别海面溢油源的正构烷烃气相色谱指纹法及其可行性和有效性，结果令人满意。该方法包括样品的前处理、GC测定和数据分析。其整个操作流程短，且较简便易行，尤其是选择正十七烷（n－C17）、正十八烷（n－C18）、姥鲛烷（pri）、植烷（phy）和正二十烷（n-C20）等特征烷烃作为判据，可信度大，对于经历一定风化作用的海面溢油仍可进行有效的鉴别。     

基于特征比值的原油中PAHs标志物风化规律研究

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。     

An experimental marine ecosystem response to crude oil and Corexit 9527: Part 2—Biological effects

Three experimental ecosystems were employed to test the effect of Corexit 9527, with and without Prudhoe Bay crude oil, on the ecology of a temperate pelagic ecosystem. The results indicated that Corexit 9527 alone enhanced biological productivity without changing the structure of the ecosystem. The mixture of Corexit and crude oil caused a major change in the ecology of the ecosystem which resulted in large numbers of bacteria and zooflagellates, but a depression of all other zooplankton phyla.     

Source diagnostic and weathering indicators of oil spills utilizing bicyclic sesquiterpanes

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.     

Bohai crude oil identification by gas chromatogram fingerprinting quantitative analysis coupled with cluster analysis

1 IntroductionWith the development of industry, more andmore petroleum energy sources are needed. The ex-ploitation of, especially benthal, develops quickly.The spilled oil accidents occur inevitably during oilexploitation and transportation. For example, in theBohai Sea, there are more than 1 000 oil wells andthe spilled oil accidents occur almost every year. Allkinds of dissension arose since the accidents couldnot be dealt with effectively in time. The key stepwhich affects the accidents …     

A field study on the acute effects of the dispersant Corexit 9527 on glucose uptake by marine microorganisms

The effects of the dispersant Corexit 9527 and Corexit with crude oil on the rate of glucose uptake and mineralisation were studied in Arctic and Subarctic marine waters and sediments. Essentially all of the 149 water and 95 sediment samples tested displayed decreased glucose uptake rates in the presence of either 15 or 50 ppm Corexit. Depressed uptake rates were observed at concentrations as low as 1 ppm. The mean concentration at which Corexit depressed glucose uptake by 50% was 12 ppm. The effect of Corexit was more pronounced on pelagic than on benthic microbial populations.