化学消油剂对原油乳化及微生物降解的影响

化学消油剂的使用已成为国内外海洋溢油事故应急处理的重要措施之一。本文分别从光明化学消油剂GM-8的用量、油水比及环境pH等方面,对正十四烷及原油乳化效果进行分析。结果表明, GM-8对正十四烷及原油的乳化效果较好,当化学消油剂的用量为原油的5%时,正十四烷及原油的乳化指数较高。在消油剂与原油用量比为一定值时,原油的乳化效果与海水的量几乎没有关系。环境pH对GM-8乳化原油的影响不大,乳化后的原油可以在海洋环境中稳定7 d以上。GM-8对原油的微生物降解有一定的增强作用。N/P、环境的pH以及微生物的接种量等均对乳化原油的生物降解有较大的影响。当微生物的接种量由培养基的1%增加到10%时,乳化原油的微生物降解率增加了一倍以上,达到91.6%。     

Detection of the water-soluble fraction of crude oil by the blue crab, Callinectes sapidus

The ability of the blue crab, Callinectes sapidus, to detect petroleum hydrocarbons was measured with behavioural techniques. When presented with a water-soluble fraction of Prudhoe Bay crude oil, blue crabs abruptly changed antennular orientation, began rhythmic beating of the maxillipedal flagellae, and increased antennular flicking rate. The threshold concentration at which 50% of the crabs detected the water-soluble fraction was 2 × 10^?6 mg/litre. The blue crab apparently can readily detect petroleum hydrocarbons at concentrations found in chronically polluted areas as well as oil spill situations.     

In situ microbial degradation of Prudhoe Bay crude oil in Beaufort Sea sediments

This study examined the fate of Prudhoe Bay crude oil in nearshore sediments of the Beaufort Sea, in situ, with emphasis on the rôle of microorganisms in the weathering process. The results indicate that oil is degraded in Arctic sediments very slowly; only after 1 year's exposure was biodegradation evident. Several factors probably contributed to the slow rate of microbial weathering, including: limited populations of hydrocarbon utilising microorganisms; localised high oil concentrations; low temperatures; limiting nutrient concentrations (unfavourable C:N and C:P ratios); low oxygen tensions and limited circulation of interstitial waters in fine-grained sediments. Abiotic weathering of the oil was also slow, with limited loss of low molecular weight aliphatic and aromatic hydrocarbons during 2 years' exposure. Significant features of the overall weathering process were: lack of initial loss of low molecular weight compounds; aliphatic compounds were not preferentially degraded over aromatic compounds and C₁₇, and lower molecular weight normal alkanes were preferentially degraded over higher molecular weight alkanes. The results of this study indicate that hydrocarbons will persist relatively unaltered for several years if Beaufort Sea sediments are contaminated with petroleum.     

Effects of dietary and water-borne oil exposure on larval pacific herring (Clupea harengus pallasi)

Pacific herring (Clupea harengus pallasi) larvae were exposed either directly to the water-soluble fraction (WSF) of crude oil or indirectly via oil-contaminated prey (OCP) (Artemia salina) for <- 28 days, to determine the relative effects of diet and water as routes of contamination. Larvae were affected rapidly by 0·9 ppm WSF, which caused high larval mortality, reduced swimming ability and rapid reductions in feeding rates. Larval length was significantly reduced by 0·7 ppm WSF in 7 days and by 0·3 ppm WSF within 14 days. The WSF exposure also caused similar reductions in larval weights. Highly contaminated prey (6 ppm prey exposure) caused significant mortality, but surviving larvae appeared robust. The OCP did not affect swimming, feeding, or growth. Exposure of larvae was not significantly extended by OCP, which rapidly depurated WSF in clean water (98% in 1 day). Therefore, OCP is probably not an important source of low molecular weight petroleum contamination to larval fish in the marine environment.     

Interactions between dissolved petroleum hydrocarbons and pure and humic acid-coated mineral surfaces in artificial seawater

The adsorption of total petroleum hydrocarbons (TPHs) on suspended particles in the marine environment is an important process affecting the fate of oils spilled in the ocean. Adsorption kinetics and adsorption isotherms of the water-soluble fraction of Fuel Oil No. 6 were performed on pure and humic acid-modified montmorillonite, alumina and kaolinite. The rates of adsorption on all sorbents are very fast and a pseudo-equilibrium is reached within 0.5 h. Linear adsorption isotherms were obtained for TPH and individual aromatic hydrocarbons on all sorbents. Higher sorption coefficients (Kd) were obtained for the humic acid-coated clays compared to the pure clays. However, a great contribution of mineral surface to overall adsorption was found on humic acid-modified particles in this study. A linear relationship between the log K and log Kow was also found for individual compounds on both pure alumina (log Km) and humic acid-coated alumina (log Koc).     

Natural seepage of crude oil into the marine environment

Recent global estimates of crude-oil seepage rates suggest that about 47% of crude oil currently entering the marine environment is from natural seeps, whereas 53% results from leaks and spills during the extraction, transportation, refining, storage, and utilization of petroleum. The amount of natural crude-oil seepage is currently estimated to be 600,000 metric tons per year, with a range of uncertainty of 200,000 to 2,000,000 metric tons per year. Thus, natural oil seeps may be the single most important source of oil that enters the ocean, exceeding each of the various sources of crude oil that enters the ocean through its exploitation by humankind.     

用长效肥料提高微生物分解海面油膜试验

氮和磷是限制海洋油污生物降解的重要因素,采用可被微生物分解的两种蜡的混合物,把含有10:1的氮和磷的无机盐粉末包埋起来,制成亲油性且能与油膜漂浮在一起的长效肥料。在室内进行促进海水表面柴油油膜的生物氧化实验,结果表明:制备的长效肥料有促进油膜中烃类氧化微生物的生长和柴油的生物降解作用,实验9天除油率达到57 4％,对照实验仅24.5％。     

Assessment of the effects of hydrocarbon contamination on the sedimentary bacterial communities and determination of the polar lipid fraction purity: Relevance of intact phospholipid analysis

This in situ study reports on the relevance of intact phospholipids as new biomarkers and highlights the limits of the classical fatty acid analysis after the hydrolysis of the polar lipid fraction. The analysis of polar lipid fractions revealed significant contributions of marine macrophytes with either non-phospholipid compounds (sulfoquinovosyl diacylglycerol) or with both non-bacterial phospholipid classes (phosphatidylcholine) and non-bacterial phospholipid molecular species (some molecular species of phosphatidylglycerol). The analysis of intact phospholipids showed also the predominance of gram-negative bacteria in sediments whereas the analysis of fatty acids alone cannot confirm such information. Lastly, as regard to the effects of petroleum hydrocarbons on the sedimentary bacterial communities, we observed a higher degree of saturation of the fatty acyl chains of the phospholipids extracted from sediment exposed to a massive and chronic crude oil contamination. Such a result was interpreted as an adaptive response resulting in higher membrane rigidity of the bacterial communities.     

舟山海洋沉积物及沿海沉积物流动相石油污染的电阻率特性及其影响因素研究

海洋沉积物作为难以降解的石油类污染物的最终归宿,其污染程度的监测至关重要。本文通过现场采集舟山海洋沉积物及沿海沉积物(包括中砂、粉砂质砂和粉砂),以流动相原油为代表,采用单因素分析法室内配制标准污染沉积物样品测定电阻率,探讨沉积物类型、含水率、含油率、时间因素对石油污染海洋及沿海沉积物的电阻率影响及变化规律。结果显示,未污染和原油污染后海洋沉积物中砂、粉砂质砂、粉砂的电阻率随含水率的升高均呈幂函数降低趋势,并符合Archie公式。在含水率15%时,电阻率随含油率总体上升;而在含水率5%时,中砂电阻率呈现一个小幅上升的趋势;粉砂电阻率先小幅下降后略上升再小幅下降,粉砂质砂电阻率则是先大幅下降后略上升再小幅下降。15%含水率污染沉积物的电阻率随时间增加持续上升;5%含水率污染沉积物电阻率先上升后略下降再大幅上升。研究成果可为海洋及沿海沉积物石油污染电阻率法快速监测提供理论支持,以期为海洋环境管理部门提供相应的决策依据。     

Petroleum contamination and biochemical alterations in oysters (Crassostrea gigas) and plaice (Pleuronectes platessa) from bays impacted by the Amoco Cadiz crude oil spill

Following the Amoco Cadiz crude oil spill in March 1978, marine animals in coastal and estuarine environments along the north shore of Brittany, France became heavily contaminated with crude oil. The resident benthic fauna in the oil-impacted area which survived the spill were severely stressed by the pollution. The objectives of our investigation were to document long-term trends in petroleum hydrocarbon contamination and sublethal stress in oysters and plaice from the estuaries, Aber Benoit and Aber Wrac'h. Oysters in the estuaries accumulated aliphatic and aromatic petroleum hydrocarbons to high levels and remained heavily contaminated for the duration of the 27 month investigation. Plaice, on the other hand, retained only low concentrations of petroleum hydrocarbons in muscle and liver tissue. Nevertheless, the oysters exhibited very few histopathologic and biochemical responses to the oil, whereas the plaice from the estuaries exhibited a variety of sublethal histopathologic and biochemical alterations.     

Degradation of crude oils byPseudomonas sp. in enriched seawater medium

Microbial degradation of five crude oils such as Arabian light, Berri, Murban, Khafji and Minas crude oil by a pure bacterial strain,Pseudomonas sp. isolated from the sea water sampled at Kawasaki Harbor in Tokyo Bay, was studied experimentally in the enriched seawater medium.The degradation of crude oils was determined in total residual oil and in four fractions of saturated, aromatics, asphaltene and column residue by use of the column chromatography with activated alumina.The saturated fraction was shown to be most biodegradable. The aromatics followed for all five crude oils examined and the asphaltene was biodegradable to some extent. The column residue was not apparently degraded byPseudomonas sp. within 30 days. Each of Arabian light, Berri or Murban crude oil was degraded from 59 to 63.5 %, Khafji crude oil 49 % and Minas crude oil, solid at room temperature, only 33 %. Degradation rate of the five crude oils was determined to be in a range from 2.88 to 17.3 mg-oil 1^–1 hr^–1 or from 6.0×10^–12 to 1.56×10^–10 mg-oil cell^–1 hr^–1. Relative degradation ofn-paraffins of different carbon numbers in the saturated fraction was found to be similar regardless of carbon number for the five crude oils.     

Effect of environmental factors on photodegradation of polycyclic aromatic hydrocarbons (PAHs) in the water-soluble fraction of Kuwait crude oil in seawater

Photodegradation of PAHs in the water-soluble fraction of Kuwait crude oil in seawater was investigated under various environmental factors (temperature, light intensity, oxygen levels and presence of a sensitizer) in laboratory conditions. All factors investigated had significant effect on the degradation rates of PAHs. At 15 °C almost all PAHs optimally degraded at an oxygen level of 4 ppm. For lower molecular weight PAHs a light intensity of 500 W/m² in the presence of the sensitizer worked well. Higher molecular weight PAHs degraded at faster rates at a light intensity 750 W/m². At 30 °C, most of the PAHs degraded optimally at an oxygen level of 0 ppm and light intensity of 500 or 750 W/m² in presence of the sensitizer. At 40 °C, most of PAHs degraded optimally at low oxygen concentrations (0 and 4 ppm) and a light intensity of 500 W/m² in the presence of the sensitizer. Linear regression indicated that for most of the compounds, light intensity had the greatest effect on degradation rates.     

Rates of microbial degradation of petroleum components as determined by computerized capillary gas chromatography and computerized mass spectrometry

The biodegradation rates of Arabian light crude oil components under the action of a marine mixed microbial culture were monitored in a quasicontinuous culture during a 60 day experiment. The saturated hydrocarbons were degraded more rapidly and extensively (74%) than the aromatics (50%), whereas the biodegradation of asphaltenes (30%) and of resins (< 5%) was very low. The joint use of computerized high-resolution chromatography and of computerized mass spectrometry permitted classification of the petroleum constituents according to their biodegradability: (i) highly susceptible, − and iso-alkanes; (ii) susceptible, 6, 1, 5 and 2 ring alkanes, 1 ring and sulphur aromatics; (iii) moderately susceptible, 3 and 4 ring alkanes, 2 and 3 ring aromatics; (iv) resistant, tetra-aromatics, steranes, triterpanes, naphtheno-aromatics; and (v) highly resistent, penta-aromatics, asphaltenes and resins. Unlike saturates, aromatics were degraded at a rate that was in relation to the number of rings of the molecules. The microbial activity leads to the formation of a residue which can be considered as a form of stable organic matter. The biodegradation potential of a mixed microflora is much more elevated in continuous culture systems than in batch cultures.     

Experimental degradation of crude oil by marine bacteria

The ability of biodegradation for crude oil was examined for ten strains of marine bacteria. With regard to their degradation ability forn-alkanes the microorganisms tested could be divided into four groups, although the same result was not observed for microbial degradation of aromatic hydrocarbons obtained by the UV measurements.     

Accumulation and depuration of petroleum hydrocarbons by black mussels. 1. Laboratory exposure trials

Laboratory experiments were conducted to measure the rates of accumulation and subsequent depuration of hydrocarbons by black mussels after exposure to various concentrations of water-soluble fractions of crude oil. The initial rate of uptake was related to the concentration in the water, but a maximum level of accumulation was found after long-term exposure. The rate of depuration was closely related to the time of exposure prior to depuration. The depuration profile consists of an initial rapid loss followed by a slower loss of the remaining hydrocarbons. Increased exposure time decreases the relative quantity of hydrocarbons lost in the initial rapid depuration. The results indicate that the use of mussels as petroleum hydrocarbon input "monitors" might have limitations.     

Laboratory investigation of single floating booms a and series of booms in the prevention of oil slick and jellyfish movement

Laboratory experiments were carried out to test the effectiveness of single floating booms, and series of barriers in preventing oil slick and jellyfish movement under various current, wind, and wave conditions. Samples of Kuwait light crude, Kuwait heavy crude, and emulsified Kuwait heavy crude oil were selected for the test program. It was found that the single floating booms were only effective in preventing the oil slick movement at current speeds less than 0.15 m/s for emulsified oil and 0.25 nits for non-emulsified oil. Double floating booms (with a distance of 16 times the boom's draught between them) prevented both non-emulsified and emulsified oil movement when current speed was less than 0.25 nits. The double floating boom system had the best performance in containing oil slick movement.In the combined air-bubble barrier and floating boom system, the air-bubble plume lifted the jellyfish to the water's surface, and thus most jellyfish accumulated in front of the floating boom. With the help of a proper collection device (such as a suction pump), the accumulated jellyfish could be removed to a desired location. Therefore, the quantity of jellyfish moving into the intake channel was reduced.Based on the test results, three different arrangements were recommended for the protection Kuwait's water intakes and harbors from oil slick and jellyfish movement.     

溢油乳化过程C波段微波散射特性实验研究

本文基于水槽溢油观测实验，研究溢油乳化过程中表面散射特性的变化。利用全极化C波段微波散射计和矢量网络分析仪等测量设备对易发生乳化反应沥青含量小于3%的原油（A型油）、油田中开采出的新鲜原油（B型油）和经过脱水去杂质处理的工业原油（C型油）进行观测。文中详细分析了在C波段微波下乳化油膜与平静水面的后向散射差异，以及油膜乳化过程对后向散射的影响，结果显示在低风速、无浪的条件下（最大波高低于3mm），原油的乳化反应可通过表面粗糙度和自身介电常数的变化来调制雷达后向散射，并且这两种方式中表面粗糙度的影响占主导地位。对比B型和C型原油在乳化状态和未乳化状态下的表面后向散射，结果显示在各状态下B型油膜表面后向散射均大于C型油，且在VV、HH、HV/VH极化方式下两者后向散射平均差异分别为2.19 dB、2.63 dB、2.21 dB，在20%油膜含水率的乳化状态下差异较未乳化状态时小，平均差异分别为0.98 dB、1.49 dB、1.5 dB，结果表明不同类型油种间由于成分和油膜属性的不同会在一定程度上导致油膜表面粗糙度存在差异，影响油膜表面后向散射。     

Photo-oxidative behaviour of crude oils relative to sea pollution: Part II. Photo-induced phase separation

A phase separation appears during the photo-oxidation of a light crude oil (Zarzaitine from Algeria), an aromatic-rich petroleum distillate, and a model mixture. Analysis by steric exclusion chromatography shows that this phenomenon is due to the formation of high molecular weight species which are insoluble in the hydrocarbon mixture. The phenomenon is linked to the radical propagation of the oxidation reaction and mainly involves the aromatic fraction. Its mechanism is discussed on the basis of experimental results.     

海绵共附生微生物中具有α-葡萄糖苷酶抑制活性菌株的筛选与初步鉴定

通过建立α-葡萄糖苷酶抑制剂筛选模型,对美国圣璜岛海域海绵共附生微生物发酵产物进行活性筛选.其中,α-葡萄糖苷酶活性测试反应体系是在96孔酶标板中进行,在α-葡萄糖苷酶浓度为0.008 U/cm3,pH值为6.8,反应温度为37℃及测定生成物波长为405 nm的基础上,优化筛选模型.结果表明,模型的最佳筛选条件:底物PNPG的浓度为10 mmol/dm3、活性测试反应时间为25min,样品溶剂DMSO含量为2%(V/V).以α-葡萄糖苷酶抑制剂阿卡波糖作为阳性对照样品,根据优化后的抑制活性筛选模型对212株海绵共附生微生物的粗提物样品进行筛选.结果表明:19株微生物的粗提物抑制率大于50%;其中,抑制活性最高的5株菌株的粗提物,在浓度为0.4、0.6、0.8 mg/cm3时,其抑制活性均在70%以上,远远高于阿卡波糖的最高抑制率58%(1.6 mg/cm3).其中菌株HY936粗提物浓度在0.4 mg/cm3时,仍具有很高的α-葡萄糖苷酶抑制率79.3%.通过16SrDNA序列测定与分析,鉴定该菌株为坚强芽孢杆菌(Bacillus firmus).坚强芽孢杆菌代谢产物能显著抑制α-葡萄糖苷酶活性,这为研制新型α-葡萄糖苷酶抑制剂提供了有力的线索,对坚强芽孢杆菌有待作进一步的研究.     

Comparison of the structures of humic acids from marine sediments and degraded field diatoms by 13C- and 1H-NMR spectroscopy

Humic acids isolated from marine sediments of the Peru continental shelf and from a degraded field diatom population dominated by the diatoms Skeletonema costatum, Nitzschia seviata and Thalassiosira sp. were characterized on the basis of infrared spectra and ¹³C- and proton-NMR spectra. Aliphatic structures were found to constitute the major fraction of humic acids and they appear to be highly branched. Carbohydrates and to a lesser extent aromatic materials, carbonyl-, ether-, alcohol- and amino groups are important contributors to the structure of marine humic acids. A close relationship was observed between the chemical structure of the sedimentary humic acid and the plankton humic acid.