Degradation ofn-paraffin mixture by marine microorganisms in enriched seawater medium

The ability to degraden-paraffin mixture of two bacterial strains,Caulobacter sp. andFlavobacterium sp., isolated from sea water of Tokyo Bay was studied experimentally in the enriched seawater (ESW) medium. These bacteria degraded actively the mixture ofn-tridecane,n-tetradecane,n-pentadecane andn-hexadecane. The maximum rate of degradation was observed after a lag period of 2 to 8 day and these bacteria were found to degrade then-paraffin mixture at rates calculated to be in a range from 3.3×10^?12 to 3.4×10^?11 mg-oil cell^?1 h^?1 at 20°C. The maximum degradation rate,r _m mg-oil l^?1 h^?1, was correlated with the amount of the initial totaln-paraffin,S mg-oil l^?1, as expressed by the following equation: $$rm = (rm)\max \left( {\frac{S}{{S + Km}}} \right)$$ where (r _m )_max denotes the largest value ofr _m whenn-paraffin exists in large excess andK _m is a constant and represents the amount ofn-paraffin at which the degradation rate,r _m , reaches 1/2 of its largest value, (r _m )_max. The values of (r _m )_max andK _m were calculated to be as follows: In the case ofCaulobacter sp. (strain KM-1), (r _m )_max=6.0 mg-oil l^?1 h^?1 andK _m =191 mg-oillesw ^?1; in the case ofFlavobacterium sp., (r _m )_max=5.47 mg-oil l^?1 h^?1 andK _m =152 mg-oillesw ^?1.     

Sensitivity of three microalgae to crude oils and fuel oils

Four crude oils and five fuel oils have been tested for toxicity with three microalgae—a blue-green, a green and a diatom. The oils were absorbed on filter paper pads and the pads submerged in the growth medium. The crude oils were less inhibitory than equal amounts of fuel oils. Despite initial growth lags, the crude oils allowed growth at 30 μl/20 ml of culture medium (10⁵ cells/ml) while fuel oils were lethal at 10 μl/20 ml. The toxicity patterns of two of the whole fuel oils were different from that seen with their water soluble fractions (WSF); for example, the Baton Rouge fuel oil sample was very toxic to growth of the three test organisms whereas its WSF was relatively innocuous. Photosynthesis of a sensitive organism Chlorella autotrophica, strain 580 (10⁷ cells/ml), was only temporarily depressed by the crude oils (30 μl/20 ml). Four of the fuel oils inhibited photosynthesis, O₂ output decreasing to zero without recovery. When the fuel oils were heated in a stream of helium they were detoxified. Chemical analyses of two of the toxic fuel oils before and after heating were compared with analyses of the Montana sample, a largely non-toxic fuel oil, in an effort to determine what types of compounds might be involved. Classes of aromatic compounds which were not accountable for the toxicity observed here include naphthalene, methylnaphthalenes, dibenzothiophenes, phenanthrenes and compounds with volatilities greater than methylnaphthalenes. Paraffinic and asphaltic fractions of fuel oil were also non-toxic. The accumulated chemical data suggest that the toxicity of whole fuel oils is due to the less water soluble types of compounds in the higher boiling aromatic fraction.     

Photo-oxidative behaviour of crude oils relative to sea pollution: Part I. Comparative study of various crude oils and model systems

The photo-oxidation of three crude oils from Algeria, the Middle East and Venezuela, respectively, is studied under conditions simulating natural ageing (λ > 300 nm, temperatures between 16 and 38°C) of oil films on the sea surface. The kinetic behaviour differs noticeably from one to another; this could be essentially due to the presence or absence of sulphur compounds. Powerful photosensitizers or photophysical stabilizers have no influence on the course of oxidation, whereas a radical trap (hindered amine) lowers the reaction rate noticeably. The study of model systems such as distillates or a synthetic mixture show the importance of polynuclear aromatics in photo-initiation and of alkyl branched aromatics in the radical propagation of oxidation chains.     

海水介质中钼酸根在针铁矿上的吸附(英文)

研究了ｐＨ 和总钼酸根浓度对海水中钼酸根在针铁矿上吸附的影响。钼酸根在针铁矿上的吸附等温线为Ｓ型。假设海水中钼酸根在针铁矿表面的吸附,是在双电层的内Ｈｅｌｍｈｏｌｔ 层中的能量相等的不同位置上进行的,并考虑到吸附的钼酸根之间存在着横向相互作用,由此推导得到的吸附等温式可描述钼酸根在针铁矿上的Ｓ型吸附等温线,并计算得到钼酸根在针铁矿上的最大吸附量为４ ．７６ ×１０－ ５ｍｏｌ／ｇ。钼酸根在针铁矿上的吸附受溶液ｐＨ影响,吸附密度随ｐＨ 的增加而降低。加入到海水中的钼约有２０ ％ 可被水合氧化铁的清除作用所转移。     

海水中沉底油的风化特性及鉴别方法研究

通过对具有代表性的两种原油和两种船用燃油进行340 d的室外模拟风化模拟实验,运用GC-FID法和同步荧光光谱法对海水中风化的漂浮油和沉底油的特性进行分析,为沉底油溯源提供相关依据,以此完善海上溢油事故的监管工作。结果表明:4种实验油品的漂浮油和沉底油荧光光谱差别不大,因此可以用荧光光谱法初步测定沉底油的风化时间;沉底油受蒸发、光解等影响弱于漂浮油,其GC可保持低碳组分峰形,并且由于生物降解,沉底油的气相谱图中均出现不可分辨的复杂混合物(UCM)的特征图谱,可以作为判断是否沉底的判据;两种方法相结合,可以建立一种确定溢油时间、风化经历及方法,以便对溢油进行更准确的溯源。     

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.     

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%.     

用含氯化镉培养液培养塔胞藻的生物学效应

在塔胞藻培养液中加入不同浓度的CdCl2,然后分析了培养在各种处理和对照组的塔胞藻后代.结果发现,随着镉离子浓度的升高,细胞的生长繁殖量和体积在前2轮(9d为一轮)培养中均明显降低,而在第3轮培养时,细胞的繁殖和大小接近常态.随后对处理后多种细胞内含物含量进行了分析,显示出:随着培养液中镉离子浓度增高,细胞内的蛋白质、叶绿素含量均明显下降,而可溶性糖、核酸的含量与对照相比变化不大.     

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.     

Degradation of lubricating oils by marine bacteria observed by quantitative mass spectrometry

Bacterial degradation of the hydrocarbons of lubricating oils was investigated by mass spectrometric analysis which gives both total amount and the composition of hydrocarbon types of residual oil. An unused lubricating oil, which mainly consisted of hydrocarbon types with only a small percentage ofn-alkanes, was degraded by marineBacillus sp. andPseudomonas sp. with 55 % and 25 % decreases in 10 days, respectively. Susceptibility of respective hydrocarbon types to biodegradation was in the following order: alkanes > non-condensed cycloalkanes, mono-aromatics > condensed cycloalkanes. A used lubricating oil of different brand showed a larger decrease than the unused oil. Both species of bacteria degraded large portions of alkane fraction of Arabian light crude oil.     

Degradation of malachite green dye by Tenacibaculum sp. HMG1isolated from Pacific deep-sea sediments

A deep-sea bacterium from the Pacific Ocean identified as Tenacibaculum sp. HMG1 was found to have strong malachite green(MG) degradation activity. The MG tolerance and decolorizing activities of strain HMG1 were confirmed by bacterial growth and high-performance liquid chromatography(HPLC) analyses. Strain HMG1 was capable of removing 98.8% of the MG in cultures within 12 h and was able to grow vigorously at 20 mg/L MG. A peroxidase gene detected in the genome of strain HMG1 was found to be involved in the MG biodegradation process. The corresponding recombinant peroxidase(r POD) demonstrated high degradative activity at 1 000 mg/L MG. Based on the common candidate intermediates, strain HMG1 was inferred to have one primary MG degradation pathway containing r POD. In addition, five other candidate intermediates of the r POD-MG degradative process were detected. The optimal conditions for MG degradation were determined and showed that strain HMG1 and the r POD enzyme could maintain high bioactivity at a low temperature(20°C), variable p H values(6.0–9.0), higher salinities(100 mmol/L) and other factors, such as multiple metal ions, H_2O_2 and EDTA.MG-tolerant strain Tenacibaculum sp. HMG1 and its peroxidase have prospective applications as environmental amendments for MG degradation during coastal remediation.     

On the formation of short-lived,toxic, water-soluble compounds during illumination of crude oil on seawater

The toxicity of various oil extracts has been studied using cod eggs as test organisms. The most toxic effect was observed when the eggs were kept underneath the water/oil interface during irradiation. This supports the notion that toxic primary photoproducts with a short life-time are generated when oil on seawater is illuminated.     

Mechanisms of petroleum accumulation in the Bozhong sub-basin, Bohai Bay Basin, China. Part 1: Origin and occurrence of crude oils

The origin of the fourteen major oil fields in the Bozhong sub-basin, Bohai Bay basin was studied based on the results of Rock-Eval pyrolysis on more than 700 samples and biomarker analysis on 61 source rock samples and 87 oil samples. The three possible source rock intervals have different biomarker assemblages and were deposited in different environments. The third member of the Oligocene Dongying Formation (E₃d₃, 32.8–30.3 Ma in age) is characterized mainly by high C₁₉/C₂₃ tricyclic terpane (>0.75), high C₂₄ tetracyclic terpane/C₂₆ tricyclic terpane (>2.5), low gammacerane/αβ C₃₀ hopane (<0.15) and low 4-methyl steranes/ΣC₂₉ steranes (<0.15) ratios, and was deposited in sub-oxic to anoxic environments with significant terrigenous organic matter input. The first (E₂s₁, 35.8–32.8 Ma) and third (E₂s₃, 43.0–38.0 Ma) members of the Eocene Shahejie Formation have low C₁₉/C₂₃ tricyclic terpane and low C₂₄ tetracyclic terpane/C₂₆ tricyclic terpane ratios and were deposited in anoxic environments with minor terrestrial organic matter input, but have different abundances of 4-methyl steranes and gammacerane. The hydrocarbon-generating potential and biomarker associations of these three source rock intervals were controlled by tectonic evolution of the sub-basin and climate changes. Three oil families derived from E₂s₃, E₂s₁ and E₃d, respectively, and three types of mixed oils have been identified. All large oil fields in the Bozhong sub-basin display considerable heterogeneities in biomarker compositions and originated from more than one source rock interval, which suggests that mixing of oils derived from multiple source rock intervals or multiple generative kitchens, and/or focusing of oils originated from a large area of a generative kitchen, is essential for the formation of large oil fields in the Bozhong sub-basin. E₂s₃- and E₂s₁-derived oils experienced relatively long-distance lateral migration and accumulated in traps away from the generative kitchen. E₃d₃-derived oils had migrated short distances and accumulated in traps closer to the generative kitchen. Such a petroleum distribution pattern has important implications for future exploration. There is considerable exploration potential for Dongying-derived oils in the Bozhong sub-basin, and traps close to or within the generative kitchens have better chance to contain oils generated from the Dongying Formation.     

太平洋深海沉积物来源的菌株Tenacibaculum sp.HMG1对孔雀石绿降解特性的研究

本文在太平洋深海沉积物中分离得到一株孔雀石绿降解菌株,鉴定命名为Tenacibaculum sp.HMG1。通过菌株生长实验和高效液相色谱的研究表明, HMG1菌株可以在20 mg/L的孔雀石绿中维持较快的生长速率,并且在12 h内可降解98.8%的孔雀石绿,这证明该菌株具有很高的孔雀石绿耐受能力和降解活性。通过基因组测序在HMG1菌株发现一条过氧化物酶基因可能参与了孔雀石绿的降解,随后利用原核表达获得了相应的重组蛋白。实验表明,该重组过氧化物酶具有极强的活性,可在1000 mg/L的孔雀石绿中发挥降解功能。本文利用液相色谱-质谱联用（LC-MS）技术对孔雀石绿的菌株降解产物和重组酶降解产物进行鉴定,并基于鉴定结果推测了两种降解途径。结果发现两种降解方式存在共同的降解途径。此外,孔雀石绿降解条件的实验结果证明重组过氧化物酶可以在低温（20℃）、复杂的pH值（6.0–9.0）、高盐度（100 mmol/L）、金属离子和EDTA等反应条件下依旧维持很高的孔雀石绿降解活性。以上实验结果表明,HMG1菌株和重组过氧化物酶均在孔雀石绿污染生物修复方面具有很大潜力。     

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.     

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。     

Characteristics and origin of carbon isotopes of n-alkanes in crude oils from the western Pearl River Mouth Basin,South China sea

The quantitative characterization of carbon isotopes of n-alkanes is commonly carried out in organic geochemical studies. Possible controls on carbon isotopes include source organic matter, maturity, fractionation during oil expulsion and migration, and the mixing of different oils. In this study of the origin of crude oils in the western Pearl River Mouth Basin, the influences of all of these factors have been considered in reaching a conclusion. Carbon isotopes of n-alkanes in the crude oils, and the extracts of the two effective source rocks (the Wenchang and Enping formations) in the basin, exhibit clear differences. The Wenchang source rocks have heavy δ¹³C values that remain almost constant or become slightly heavier with increasing carbon number. The Enping source rocks have light δ¹³C values that become lighter with increasing carbon number. Two groups of oils in this area were identified based on the carbon isotopes of the n-alkanes; groupIoils are similar to extracts of the Wenchang source rocks. However, the groupIIoils are different from both the Wenchang and Enping source rocks and the carbon isotopic profiles of their n-alkanes exhibit a “V” feature with increasing carbon number. The results of artificial thermal maturation experiments indicate that, from the early stage to the peak stage of oil generation (with EasyRo between 0.64% and 1.02%), the δ¹³C values of n-alkanes in the pyrolysis oils become heavier by about 3‰ with increasing thermal maturity, but the shape of the carbon isotopic profiles are not significantly changed. Calculated δ¹³C values of n-alkanes in “mixed” artificial pyrolysis oils indicate that the mixture of oils generated from the same source rocks with different maturities could not change the carbon isotopic profile of the n-alkanes, however, a mixing of the Wenchang and Enping oils could give the “V” feature in the profiles, similar to the groupIIoils in this area. The groupIIoils appear to be mixed Wenchang and Enping oils, the latter being the dominant component in the mixture. We conclude that the source organic matter and the degree of mixing are the main factors controlling the carbon isotopic characteristics of n-alkanes in crude oils in the western Pearl River Mouth Basin.     

Organic geochemistry of the Silurian Tanezzuft Formation and crude oils,NC115 Concession,Murzuq Basin,southwest Libya

Thirty-six Silurian core and cuttings samples and 10 crude oil samples from Ordovician reservoirs in the NC115 Concession, Murzuq Basin, southwest Libya were studied by organic geochemical methods to determine source rock organic facies, conditions of deposition, thermal maturity and genetic relationships. The Lower Silurian Hot Shale at the base of the Tanezzuft Formation is a high-quality oil/gas-prone source rock that is currently within the early oil maturity window. The overall average TOC content of the Hot Shale is 7.2 wt% with a maximum recorded value of 20.9 wt%. By contrast, the overlying deposits of the Tanezzuft Formation have an average TOC of 0.6 wt% and a maximum value of 1.1 wt%. The organic matter in the Hot Shale consists predominantly of mixed algal and terrigenous Type-II/III kerogen, whereas the rest of the formation is dominated by terrigenous Type-III organic matter with some Type II/III kerogen. Oils from the A-, B- and H-oil fields in the NC115 Concession were almost certainly derived from marine shale source rocks that contained mixed algal and terrigenous organic input reflecting deposition under suboxic to anoxic conditions. The oils are light and sweet, and despite being similar, were almost certainly derived from different facies and maturation levels within mature source rocks. The B-oils were generated from slightly less mature source rocks than the others. Based on hierarchical cluster analysis (HCA), principal component analysis (PCA), selected source-related biomarkers and stable carbon isotope ratios, the NC115 oils can be divided into two genetic families: Family-I oils from Ordovician Mamuniyat reservoirs were probably derived from older Palaeozoic source rocks, whereas Family-II oils from Ordovician Mamuniyat–Hawaz reservoirs were probably charged from a younger Palaeozoic source of relatively high maturity. A third family appears to be a mixture of the two, but is most similar to Family-II oils. These oil families were derived from one proven mature source rock, the Early Silurian, Rhuddanian Hot Shale. There is a good correlation between the Family-II and -III oils and the Hot Shale based on carbon isotope compositions. Saturated and aromatic maturity parameters indicate that these oils were generated from a source rock of considerably higher maturity than the examined rock samples. The results imply that the oils originated from more mature source rocks outside the NC115 Concession and migrated to their current positions after generation.     

Ionization of water in seawater

The ion product of water in seawater and the total activity coefficients of hydroxide and hydrogen ions were determined over the temperature range 2° to 35°C, and the salinity range 20‰ to 44‰. At 25°C and 35‰ salinity, the measured values are pK_W^SW = 13.20, f_OH = 0.22, f_H = 0.71 on the molar concentration scale.     

Origin of crude oils from oilfields in the Zagros Fold Belt,southern Iraq: Relation to organic matter input and paleoenvironmental conditions

Crude oil samples from Cretaceous and Tertiary reservoir sections in the Zagros Fold Belt oil fields, southern Iraq were investigated using non-biomarker and biomarker parameters. The results of this study have been used to assess source of organic matter, and the genetic link between oils and their potential source rocks in the basin. The oils are characterized by high sulphur and trace metal (Ni, V) contents and relatively low API gravity values (17.4–22.7° API). This indicates that these oils are heavy and generated from a marine source rock containing Type II-S kerogen. This is supported by their biomarker distributions of normal alkanes, regular isoprenoids, terpanes and steranes and the bulk carbon isotope compositions of their saturated and aromatic hydrocarbons. The oils are characterized by low Pr/Ph ratios (<1), high values of the C₃₅ homohopane index and C₃₁-22R/C₃₀ hopane ratios, relatively high C₂₇ sterane concentrations, and the predominance of C₂₉-norhopane. These biomarkers suggest that the oils were generated predominantly from a marine carbonate source rock, deposited under reducing conditions and containing plankton/algal and microorganisms source input. The presence of gammacerane also suggests water column stratification during source rock deposition.The biomarker characteristics of the oils are consistent with those of the Middle Jurassic Sargelu carbonate as the effective source rock in the basin. Biomarker maturity data indicate that the oils were generated from early maturity source rocks.