Photochemically induced interactions in Ekofisk crude oil

Evidence for photochemically induced interactions in Ekofisk crude oil as a thin film on top of a water surface has been obtained by isotopic labelling experiments and field desorbtion mass spectrometry. The interaction behaviour to the high molecular weight resin/asphaltene material has been discussed by invoking the concept of molecular assemblies like micelles and vesicles. This latter chromophoric material has also been shown to have an appreciable sensitizing effect, resulting in a substantial transformation of carbon 14 radiolabelled species, including straight chain n-alkanes.Isotopic studies do not provide evidence for interactions in Ekofisk crude oil constituents kept in darkness, where only a very slow transformation/degradation of oil components has been observed.The implication of these findings has been discussed.     

A protocol for assessing the effectiveness of oil spill dispersants in stimulating the biodegradation of oil

Dispersants are important tools in oil spill response. Taking advantage of the energy in even small waves, they disperse floating oil slicks into tiny droplets (<70 μm) that entrain in the water column and drift apart so that they do not re-agglomerate to re-form a floating slick. The dramatically increased surface area allows microbial access to much more of the oil, and diffusion and dilution lead to oil concentrations where natural background levels of biologically available oxygen, nitrogen, and phosphorus are sufficient for microbial growth and oil consumption. Dispersants are only used on substantial spills in relatively deep water (usually >10 m), conditions that are impossible to replicate in the laboratory. To date, laboratory experiments aimed at following the biodegradation of dispersed oil usually show only minimal stimulation of the rate of biodegradation, but principally because the oil in these experiments disperses fairly effectively without dispersant. What is needed is a test protocol that allows comparison between an untreated slick that remains on the water surface during the entire biodegradation study and dispersant-treated oil that remains in the water column as small dispersed oil droplets. We show here that when this is accomplished, the rate of biodegradation is dramatically stimulated by an effective dispersant, Corexit 9500®. Further development of this approach might result in a useful tool for comparing the full benefits of different dispersants.     

Dispersibility of crude oil in fresh water

The effects of surfactant composition on the ability of chemical dispersants to disperse crude oil in fresh water were investigated. The objective of this research was to determine whether effective fresh water dispersants can be designed in case this technology is ever considered for use in fresh water environments. Previous studies on the chemical dispersion of crude oil in fresh water neither identified the dispersants that were investigated nor described the chemistry of the surfactants used. This information is necessary for developing a more fundamental understanding of chemical dispersion of crude oil at low salinity. Therefore, we evaluated the relationship between surfactant chemistry and dispersion effectiveness. We found that dispersants can be designed to drive an oil slick into the freshwater column with the same efficiency as in salt water as long as the hydrophilic-lipophilic balance is optimum.     

Enhanced reductive dechlorination in columns treated with edible oil emulsion

The effect of edible oil emulsion treatment on enhanced reductive dechlorination was evaluated in a 14 month laboratory column study. Experimental treatments included: (1) emulsified soybean oil and dilute HCl to inhibit biological activity; (2) emulsified oil only; (3) emulsified oil and anaerobic digester sludge; and (4) continuously feeding soluble substrate. A single application of emulsified oil was effective in generating strongly reducing, anaerobic conditions for over 14 months. PCE was rapidly reduced to cis-DCE in all three live columns. Bioaugmentation with a halorespiring enrichment culture resulted in complete dechlorination of PCE to ethene in the soluble substrate column (yeast extract and lactate). However, an additional treatment with a pulse of yeast extract and bioaugmentation culture was required to stimulate complete dechlorination in the emulsion treated columns. Once the dechlorinating population was established, the emulsion only column degraded PCE from 90-120 microM to below detection with concurrent ethene production in a 33 day contact time. The lower biodegradation rates in the emulsion treated columns compared to the soluble substrate column suggest that emulsified oil barriers may require a somewhat longer contact time for effective treatment. In the HCl inhibited column, partitioning of PCE to the retained oil substantially delayed PCE breakthrough. However, reduction of PCE to more soluble degradation products (cis-DCE, VC and ethene) greatly reduced the impact of oil-water partitioning in live columns. There was only a small decline in the hydraulic conductivity (K) of column #1 (low pH+emulsion, K(final)/K(initial)=0.57) and column #2 (live+emulsion, K(final)/K(initial)=0.73) indicating emulsion injection did not result in appreciable clogging of the clayey sand. However, K loss was greater in column #3 (sludge+emulsion, K(final)/K(initial)=0.12) and column #4 (soluble substrate, K(final)/K(initial)=0.03) indicating clogging due to biomass and/or gas production can be significant.     

饮食业复合油烟吸收剂的研制开发

分析了饮食油烟的成分 ,结合饮食油烟气的治理方法 ,采用正交设计法进行新型复合油烟吸收剂的实验 ,快速、有效、准确地优化确定了油烟吸收剂的配方和工艺 ,并设计了该吸收剂的油污相溶性、环境毒性、生物降解性实验 ,科学地论证了该产品的性能。结果表明 ,本实验研制的油烟吸收剂能够全面包络、粘合、皂化、附着和分离油烟废气中的油类物质 ,对饮食油烟具有快速、高效、彻底的治理效果 ,而且无毒、易降解。     

强化生物通风修复过程中柴油衰减规律及其影响因素研究

强化生物通风技术对于修复因地下储油罐泄漏引起的土壤污染具有很大的应用前景。通过室内土柱模拟柴油泄漏污染土壤,从土柱中总石油烃（total petroleum hydrocarbon,TPH）剖面分布随时间的变化及降解模式角度,分析了其自然衰减和强化生物通风过程。结果表明：初始柴油浓度直接影响着各柱在自然衰减和强化生物通风过程中柱内的残余TPH平衡分布曲线的形状和浓度峰值位置;在前期自然衰减过程中（约1个月）,当土壤中的柴油浓度为5 000～40 000 mg油/kg土时,整个柱内TPH变化的主要原因是重力扩散迁移的结果;当土壤中的柴油浓度≤5 000 mg油/kg土时,其TPH的变化不仅是重力扩散迁移作用的结果,生物降解作用也存在;通风约2个月后,抽提作用对于保持土柱上部柴油浓度稳定变化的意义较为突出。     

Tween-80和H2O2对Burkholderia cepacia降解油脂的影响

油脂废水是一种重要的水污染源。研究了表面活性剂和H₂O₂对洋葱伯克霍尔德氏菌(Burkholderia cepacia)降解油脂的影响。结果表明：适量的表面活性剂和H₂O₂促进油脂的降解。表面活性剂可以增强油脂在水相中的溶解度，提高油脂在水中的乳化程度从而增加其生物可利用性。当Tween-80浓度600mg/L时，油脂降解率达到91%。低浓度H₂O₂不仅能刺激微生物生长，而且使培养液中的pH值保持相对稳定，提高了微生物对油脂的降解率。H₂O₂在浓度为400mg/L时，能使油脂降解率达到90%。     

固定化原油降解菌的制备及其性能研究

从石油污染土壤中筛选出的石油降解菌Y-13对石油的降解率为57.45%,经初步鉴定为芽孢杆菌属,以Y-13为固定化对象,选择聚乙烯醇(PVA)、海藻酸钠(SA)为主要载体材料,以胜利原油为反应底物,研究了固定化微球的制备和运行条件对微球性能的影响,实验确定了PVA-H3BO3包埋法制备固定化微球的最佳条件,最高降解率为79.04%;对PVA-H3BO3微球的性能测定结果表明:这种固定化微球具有良好的机械强度、弹性和渗透性、较高的比表面积和孔容;固定化微球比游离细菌对外界的适应性要强,适宜pH值、接种量和活化时间分别为7.5、1∶10和21 h。     

Removal by sorption and in situ biodegradation of oil spills limits damage to marine biota: a laboratory simulation

This study examined the efficiency of cotton grass fibers in removing diesel oil from the surface of water in conditions prevailing in the Baltic Sea. The effect of low temperature, salinity, and bacterial amendments were tested in laboratory-scale set-ups, whereas 600-L mesocosms filled with Baltic Sea water were used for testing the effects of diesel oil and rapid removal of the oil on microorganisms, phytoplankton, and mussels. Cotton grass proved to be an excellent sorbent for diesel oil from the water surface at a low temperature. Inoculation with diesel-enriched microorganisms enhanced degradation of oil significantly in laboratory-scale experiments. In mesocosm experiments, the addition of diesel oil (0.66 mg L(-1), 0.533 L m(-2)) to the basins resulted in higher microbial density than in all other basins, including inoculated ones, suggesting that the Baltic Sea contains indigenous hydrocarbon degraders. The removal of oil with cotton grass significantly improved the survival of mussels in the mesocosm tests: 100% mortality in diesel basins versus 0% mortality in basins with cotton grass, respectively. However, the surviving mussels suffered from histopathological changes such as inflammatory responses, degenerations, and cell death. The observed rescuing effect was observable even when the cotton grass-bound oil was left in the water. The results underline the importance of rapid action in limiting damage caused by oil spills.     

Effective oil removal from water by magnetically driven superhydrophobic and oleophilic magnetic titania nanotubes

Development of efficient techniques to combat the harmful effects of oil spill is an emerging field, where fabrication of new sorbents for selective removal of oil has become a hot topic for environmental scientists. The present study reports the preparation of superhydrophobic/oleophilic magnetic titania nanotubes via a facile hydrothermal method, followed by the treatment with octadecylamine, as potential magnetically driven sorbent for selective removal of oil from water surface. The magnetic nature (superparamagnetism at 300 K) of the nanotubes enabled magnetic removal of the oil-sorbed material from water surface. Wettability test of the material depicted a static water contact angle of 166 ± 1°, indicating its superhydrophobic character. Oil uptake experiments and contact angle measurements revealed its superoleophilicity with maximum oil sorption capacity >1.5 g/g for a variety of oils. In addition to the ease of magnetic removal, the nanotubes possess sufficient buoyancy, high selectivity, and quick rate of oil uptake and is more than five times reusable.     

Vertical distribution of aliphatic and aromatic hydrocarbons in mussels from the Amposta offshore oil production platform (Western Mediterranean)

The qualitative distributions of aliphatic hydrocarbons in mussels adhered to the legs of an oil production platform (Amposta, Western Mediterranean) have evidenced local (diesel oil) and chronic inputs (middle East crude oils) as the main pollutant sources in the area. Quantitative data have shown that aromatic hydrocarbons are selectively accumulated with the age of mussels and are more evenly distributed through the water column. Background concentrations of petrogenic aliphatic hydrocarbons in mussels living in the vicinity of oil platforms have been established in the range of 25–40 ug/g dry weight.     

A multiple testing approach for hazard evaluation of complex mixtures in the aquatic environment: the use of diesel oil as a model

Traditional single species toxicity tests and multiple component laboratory-scaled microcosm assays were combined to assess the toxicological hazard of diesel oil, a model complex mixture, to a model aquatic environment. The immediate impact of diesel oil dosed on a freshwater community was studied in a model pond microcosm over 14 days: a 7-day dosage and a 7-day recovery period. A multicomponent laboratory microcosm was designed to monitor the biological effects of diesel oil (1.0 mg litre(-1)) on four components: water, sediment (soil + microbiota), plants (aquatic macrophytes and algae), and animals (zooplanktonic and zoobenthic invertebrates). To determine the sensitivity of each part of the community to diesel oil contamination and how this model community recovered when the oil dissipated, limnological, toxicological, and microbiological variables were considered. Our model revealed these significant occurrences during the spill period: first, a community production and respiration perturbation, characterized in the water column by a decrease in dissolved oxygen and redox potential and a concomitant increase in alkalinity and conductivity; second, marked changes in microbiota of sediments that included bacterial heterotrophic dominance and a high heterotrophic index (0.6), increased bacterial productivity, and the marked increases in numbers of saprophytic bacteria (10 x) and bacterial oil degraders (1000 x); and third, column water acutely toxic (100% mortality) to two model taxa: Selenastrum capricornutum and Daphnia magna. Following the simulated clean-up procedure to remove the oil slick, the recovery period of this freshwater microcosm was characterized by a return to control values. This experimental design emphasized monitoring toxicological responses in aquatic microcosm; hence, we proposed the term 'toxicosm' to describe this approach to aquatic toxicological hazard evaluation. The toxicosm as a valuable toxicological tool for screening aquatic contaminants was demonstrated using diesel oil as a model complex mixture.     

Influence of salinity on bioremediation of oil in soil

Spills from oil production and processing result in soils being contaminated with oil and salt. The effect of NaCl on degradation of oil in a sandy-clay loam and a clay loam soil was determined. Soils were treated with 50 g kg(-1) non-detergent motor oil (30 SAE). Salt treatments included NaCl amendments to adjust the soil solution electrical conductivities to 40, 120, and 200 dS m(-1). Soils were amended with nutrients and incubated at 25 degrees C. Oil degradation was estimated from the quantities of CO(2) evolved and from gravimetric determinations of remaining oil. Salt concentrations of 200 dS m(-1) in oil amended soils resulted in a decrease in oil mineralized by 44% for a clay loam and 20% for a sandy-clay loam soil. A salt concentration of 40 dS m(-1) reduced oil mineralization by about 10% in both soils. Oil mineralized in the oil amended clay-loam soil was 2-3 times greater than for comparable treatments of the sandy-clay loam soil. Amending the sandy-clay loam soil with 5% by weight of the clay-loam soil enhanced oil mineralization by 40%. Removal of salts from oil and salt contaminated soils before undertaking bioremediation may reduce the time required for bioremediation.     

Influence of modified soils on the removal of diesel fuel oil from water and the growth of oil degradation micro-organism

Three soils were modified with two kinds of cationic surfactants in order to increase their sorptive capabilities for organic contaminants. Sorption of diesel fuel oil in water by these modified soils had been investigated. Modified soils can effectively sorb diesel fuel oil from water. The sorption capability of modified soils is: HDTMA-black soil > HDTMA-yellow brown soil > HDTMA-red soil > TMA-black soil > TMA-yellow brown soil > TMA-red soil. Sorption of diesel fuel oil by natural soils and HDTMA modified soils is via partition, the sorption isotherms can be expressed by Henry equation, and logK(SOM) is 2.42-2.80, logK(HDTMA) is 3.37-3.60. Sorption isotherms of TMA modified soils can be expressed by Langmuir equation, the saturation sorption capacities are 1150 (TMA-black soil), 750 (TMA-yellow-brown soil), 171 mg/kg (TMA-red soil), respectively. A diesel fuel oil degradation micro-organism (Pseudomonas sp.) was isolated in the lab. To test the influence of the modified soils on the micro-organism, various growth curves of Pseudomonas in different conditions were drawn. Pseudomonas can grow very well with natural soils and TMA modified soils. The acclimation period of Pseudomonas is reduced. As to HDTMA modified soils, HDTMA loading amount is very important. When HDTMA loading amount is no higher than 0.5 CEC, the micro-organism can grow very well after a long acclimation period.     

Effects of bioturbation on the fate of oil in coastal sandy sediments--an in situ experiment

Effects of bioturbation by the common lugworm Arenicola marina on the fate of oil hydrocarbons (alkanes and PAHs) were studied in situ during a simulated oil spill in a shallow coastal area of Roskilde fjord, Denmark. The fate of selected oil compounds was monitored during 120 d using GC-MS and bioturbation activity (feces production and irrigation) was measured regularly during the experiment and used as input parameters in a mechanistic model describing the effects of A. marina on the transport and degradation of oil compounds in the sediment. The chemical analytical data and model results indicated that A. marina had profound and predictable effects on the distribution, degradation and preservation of oil and that the net effect depended on the initial distribution of oil. In sediment with an oil contaminated subsurface-layer A. marina buried the layer deeper in the sediment which clearly enhanced oil persistence. Conversely, A. marina stimulated both the physical removal and microbial degradation of oil compounds in uniformly oil contaminated sediments especially in deeper sediment layers (10-20 cm below the surface), whereas the fate of oil compounds deposited in surface layers (0-5 cm) mainly was affected by removal processes induced by wave actions and other bioturbating infauna such as Nereis diversicolor, Corophium volutator and Hydrobia spp. present in the experimental plots.     

Fast preparation of the seawater accommodated fraction of heavy fuel oil by sonication

The seawater accommodated fraction (SWAF) of oil is widely used for the assessment of its toxicity. However, its preparation in the laboratory is time consuming, and results from different authors are difficult to compare as preparation methods vary. Here we describe a simple and fast set up, using sonication, to produce reproducible SWAF in the laboratory. The system was tested on heavy fuel oil placed on seawater at different salinity and temperature conditions. Maximum dissolution of the oil was achieved after 24 h, independently of both seawater salinity and temperature. Our findings are discussed in relation to the fate of the oil from the deep spill of the Prestige tanker. Changes in temperature in the open ocean are bound to have larger impact in the concentration of the SWAF than the corresponding values of sea water salinity. We anticipate that in this type of incident the highest SWAF, as the oil reaches the sea surface, should be expected in the warmest and less saline waters of the water column.     

Stigmastane and hopanes as conserved biomarkers for estimating oil biodegradation in a former refinery plant-contaminated soil

In the last decade, a refinery plant located in Lido Adriano, East Ravenna (Italy) has been subject to mineral oil contamination. The mineral crude oil, extracted from the offshore in Adriatic sea, consisted of 78% aliphatics, cyclic alkanes and saturated polycyclic hydrocarbons, 9% aromatics, polycyclic aromatic hydrocarbons (PAHs) and alkylated derivatives, and 13% of tars/asphaltenes. Analysis of soil after 10 years of natural attenuation revealed a complete depletion of linear (n-C(9)-C(24)), light aromatics (C1-C3/benzenes) and PAHs (C2/naphthalene, C1/phenanthrene); besides a substantial degradation of isoprenoids prystane and phytane, branched and cyclic alkanes. The remaining contaminants which withstood to natural degradation was saturated polycyclic hydrocarbons (perhydro-PAH derivatives), unsaturated polycyclic hydrocarbons (tetrahydro, dihydro-PAH derivatives), terpanes, steranes and unidentified compounds. Such residues resulted in 80% reduction of its concentration after two months of laboratory treatment. Samples were extracted by organic solvents, separated by silica/alumina gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Identification and quantification of aliphatic, cyclic alkanes, typical PAHs, terpanes and steranes were carried out to chromatograms of M/Z=85, 83, individual M/Zs, M/Z=191 and 217, respectively. The present work shows that, among numerous biomarkers present in the source oil, stigmastane and two isomers of hopane showed invariable concentrations after laboratory experiments that mimic natural biodegradation in the field, so they can be used as conserved internal biomarkers. These are very useful tools to assess alterations in less stable classes of saturated compounds contained in petroleum. Marked degradation of perhydro, tetrahydro, dihydro-PAH derivatives in the laboratory treatment has been evidenced.     

利用生物柴油去除滨海构筑物上原油的模拟研究简

溢油向岸滩漂移会造成海岸带人工构筑物的严重污染。采用混凝土片模拟滨海构筑物,研究投加生物柴油及营养对石油污染物的去除效果。结果表明,施加生物柴油可以促进滨海构筑物上的石油进入水中,生物柴油施加量越大,构筑物上残余的石油量越小;同时施加生物柴油和营养能够促进海水中降解石油微生物的增殖和石油的降解;营养和微生物条件一致的情况下,投加2 mL和5 mL生物柴油的系统中石油的总去除率分别为37.5%和32.7%,表明生物柴油的投加量有一个适宜值。研究结果可为生物柴油-营养联合修复石油污染海岸带提供数据支持。     

油污土壤中微生物数量变化与原油降解速率关系的实验研究

微生物法治理油污土壤具有成本低、效果好的特点 ,其原理是微生物利用油烃作为碳源合成自身物质 ,进行生长繁殖 ,从而使油烃的含量得到减少。而与此同时 ,微生物的数量也会发生相应的变化。目前油污土壤微生物的研究主要局限于对污染土壤中分离提纯的单一菌种的降解效能的研究。本文对土著油污土壤微生物在适宜条件下的数量和种类变化进行了实验分析 ,并对油烃的化学组成作了初步探讨。分离出 4株对石油具有耐受性和降解能力的微生物。结果表明 ,在 4株微生物数量都增加的时候 ,石油烃的降解速度最快。     

Influence of oil contamination levels on hydrocarbon biodegradation in sandy sediment

The influence of oil concentration on hydrocarbon biodegradation in a sandy sediment was studied in polyvinyl chloride reactors (0.45 x 0.28 x 0.31 m) containing 76.8 kg of beach sand in natura, where the upper layer was artificially contaminated with petroleum. The oil-degrading microorganisms used consisted of a mixed culture named ND, obtained from landfarming and associated with indigenous microorganisms. On the 28th day of the process, the degradation in reactors containing sandy sediment contaminated with light Arabian oil and presenting an initial oil content of 14, 21 or 28 g kg-1 reached the following levels (%): 33.7, 32.9 and 28.9 for oil and grease; up to 88.3, 35.3 and 13.0 for C14-C26 n-alkanes; and 100, 61.3 and 59.4 for pristane, respectively. Phytane removal (37.1%) was only detected in the reactor contaminated with the lowest oil concentration studied. These results, together with the expressive bacterial growth observed (from 10(6) to 10(11) cfu g-1) give strong support to the argument that biodegradation was the dominant component of the remediation process. Susceptibility to biodegradation was inversely proportional to increasing oil contamination. The degradation of branched alkane: pristane was not repressed by the presence of n-alkanes.