Factors affecting photooxidation of oil constituents in the marine environment. I. Photochemical transformations of dimethylnaphthalenes in an aqueous environment in the presence and absence of oil

Photooxidation studies of 1,3-, 1,4-, 1,8- and 2,3-dimethylnaphthalene (DMN) suspended in and layered on seawater and distilled water have been performed in the presence and absence of crude Ekofisk oil, methylene blue and dibenzothiophene. With the exception of 2,3-DMN which was very insensitive to the reaction conditions, the course of reaction was, generally, influenced by the structure of the substrate, the salinity of the water, the oil and the presence of sulfur-containing compounds. In the absence of oil the photooxidation was fairly inefficient and took place exclusively in benzylic positions. In the presence of oil oxidation of the naphthalene moiety predominated due to abundant formation of singlet oxygen.     

Influence of synthetic and biogenic surfactants on the toxicity of water-soluble fractions of hydrocarbons in sea water determined with the bioluminescence inhibition test

The influence of increasing amounts of surfactants on the toxicity of hydrocarbons was determined using the bioluminescence inhibition test (Microtox test). Three biogenic and three synthetic surfactants were tested against the water-soluble fractions (WSF) of crude and weathered Ekofisk oil, phenol, and naphthalene. Surfactant concentrations below 100 mg litre(-1) lowered the toxicity of the WSF, indicating an antagonistic interaction reducing the toxicities of surfactants and hydrocarbons. At concentrations greater than 100 mg litre(-1) the toxicity rose again and was higher than the untreated WSF. The point of reversal seemed to be the critical micelle concentration, at which the formation of oil/water emulsions is possible.     

Treatment of oil spill by sorption technique using fatty acid grafted sawdust

Treatment of oil spills remains a challenge to environmental scientists and technologists. Among all the existing techniques used for oil treatment, sorption is a popular technique because it is cheap, simple and effective. Among the various sorbents used, sawdust appears to be the most attractive material in terms of cost, versatility and abundance. In the present work, the efficacy of surface modification of sawdust by fatty acids (oleic acid, stearic acid and decanoic acid) and vegetable oils (castor oil or mustard oil) is demonstrated. Sorption of seawater contaminated with crude oil and also weathered oil was greatly enhanced by the surface modification. The results show that oleic acid grafted sawdust (OGSD) has the best sorption capacity for crude oil as well as weathered oil.     

Interactive factors leading to dying-off Carex tato in Momoge wetland polluted by crude oil, Western Jilin, China

Momoge wetland is an internationally important wetland not only because it is a habitat for many rare bird species but also because it is an internationally important stopover for some rare global migratory bird species. However the petroleum exploitation in wetland has brought about many environmental problems. One of the most severe problems is crude oil pollution, which has caused the dying-off Carex tato and imposes great threat on survival of rare birds. This work studied the factors that caused the dying off of Carex tato. The results showed that death of Carex tato was the result narcosis toxicity of alcohols, intermediate biodegradation products of crude oil, on the root tissue, and the fragmentization of cuticle of leaves by light components of crude oil volatized from soil surface. However, the mechanism involved was much more complex and three interactive factors including crude oil pollution of soil, long-term drought and poor permeability of soil were responsible for the dying-off of Carex tato grassland. The distribution of crude oil in soil profile was characterized with high concentrations at top silty layer and the layer below root zone and low or no crude oil at root zone layer. This distribution was relative to root system characteristics and rhizospheric biodegradation. In root zone, substantive oxygen could be transported to root zone through dense root system and well developed aerenchyma. The crude oil in root zone was easily biodegraded by aerobic rhizosphere microbes. However, some toxic intermediate products, such as some alcohols, was sealed in root zone due to poor permeability of the top soil layer and the deeper soil layer and they had lethal effects on root tissue. Above ground, low molecular components of crude oil in top soil layer was easily volatized into atmosphere during long-term drought. Some of the volatized components were adsorbed onto leaves. SEM analysis showed that these components destroyed the leaves by fragmentization of cuticle of leave. This study also shows that although wetland has natural attenuation of pollutants, natural attenuation of pollutants by natural wetland should not be overemphasized. This attenuation function may lose under some conditions such as long-term drought and poor soil texture.     

Measurement of fluorescence decay of crude oil: a potential technique to identify oil slicks

The single photon counting technique has been used to measure the decay time for several Kuwaiti crude and refined oils. Fluorescent characteristics of two different bunker oils from widely separate geographic areas have been studied. Laser induced fluorescent data for the crude oil samples are compared with the decay time results to evaluate the potential of these techniques for the identification of oil sticks in the marine environment. Response of the oil film thickness to various excitation wavelengths from a CW Ar ion laser and a pulsed xenon lamp has been investigated.     

Air bubble and oil droplet interactions in centrifugal fields during air-sparged hydrocyclone flotation

The interactions of air bubbles and oil droplets in centrifugal flotation have been considered with respect to process conditions present during Air-sparged Hydrocyclone (ASH) flotation. Encounter efficiency of oil droplets with air bubbles has been found to be significantly smaller when compared to encounter efficiency of mineral particles. Collision and sliding contact times have been determined. Collision has been found to be insufficient for successful contact between oil droplets and air bubbles while sliding allows for film rupture depending on specific system conditions. Although the tenacity of oil droplet attachment to an air bubble is believed to be greater than the tenacity of a mineral particle, emulsification makes oil flotation in centrifugal devices with large dissipation of energy inefficient and hence requires the use of high molecular weight polymeric flocculants.     

炼厂"三泥"的生物处理研究

从大港油田筛选和分离出3株以原油为碳源的石油降解菌,初步鉴定为假单胞菌属(Pseudomonas sp.),用这3株菌混合处理某炼厂的"三泥",在适宜的降解条件下,仅需投加混合菌液,无需添加营养物(N,P),可使含油污泥A的残油量从67g/kg降至7.7g/kg,混合油泥试样AB的残油量从19.7g/kg降至3.1g/kg,平均去除率为84%以上,可以实现含油污泥的较为经济的、有效的处理.经生物处理后含油污泥的恶臭味完全消失.     

Oil spill cleanup using graphene

In this article, we study the use of thermally reduced graphene (TRG) for oil spill cleanup. TRG was synthesized by thermal exfoliation of graphite oxide and characterized by X-ray diffusion, Raman spectroscopy, SEM, TEM, elemental analysis, and Brunauer–Emmett–Teller (BET) surface area measurement. Various aspects of the sorption process have been studied including the sorption capacity, the recovery of the adsorbed oil, and the recyclability of TRG. Our results shows that TRG has a higher sorption capacity than any other carbon-based sorbents, with sorption capacity as high as 131 g of oil per gram TRG. With recovery of the sorbed oil via filtration and reuse of TRG for up to six cycles, 1 g of TRG collectively removes approximately 300 g of crude oil. Moreover, the effects of TRG bulk density, pore volume, and carbon/oxygen ratio and the oil viscosity on the sorption process are also discussed.     

Source diagnostic and weathering indicators of tar balls utilizing acyclic, polycyclic and S-heterocyclic components

This study represents a forensic chemical analysis to define the liability for the coastal bitumens polluting the beaches of the Mediterranean city of Alexandria. Six tar balls collected from several locations along the coast of the city were analyzed for their acyclic and polycyclic hydrocarbons as well as sulfur heterocycles using GC/FID, GC/AED and gas chromatography/mass spectrometry techniques. The analysis of one Egyptian crude oil is also included as a possible source oil. The tar ball samples were at early stages of weathering. Based on the GC traces and biomarker signatures, the tar balls could be genetically different. One sample collected from the Eastern Harbor region appears to be a Bunker C type fuel produced from Egyptian crudes. The refining process has removed the low molecular weight components. On the other hand, the wide n-alkane distribution together with the absence of an unresolved complex mixture suggests that crude oils probably from tank washings, ballast discharges or accident spills from tankers could have contributed significantly to the other tar ball samples. The distribution of source specific hopane and sterane markers revealed that the tar samples probably originate from different oil fields.     

Effect of crude oil contamination on the chlorophyll content and morpho-anatomy of Cyperus brevifolius (Rottb.) Hassk

Chlorophyll plays a pivotal role in the plant physiology and its productivity. Cultivation of plants in crude oil contaminated soil has a great impact on the synthesis of chlorophyll pigment. Morpho-anatomy of the experimental plant also shows structural deformation in higher concentrations. Keeping this in mind, a laboratory investigation has been carried out to study the effect of crude oil on chlorophyll content and morpho-anatomy of Cyperus brevifolius plant. Fifteen-day-old seedling of the plant was planted in different concentrations of the crude oil mixed soil (i.e., 10,000, 20,000, 30,000, 40,000, and 50,000 ppm). A control setup was also maintained without adding crude oil. Results were recorded after 6 months of plantation. Investigation revealed that there is a great impact of crude oil contamination on chlorophyll content of the leaves of the experimental plant. It also showed that chlorophyll a, chlorophyll b, and total chlorophyll content of leaves grown in different concentrations of crude oil were found to be lower than those of the control plant. Further, results also demonstrated that chlorophyll content was lowest in the treatment that received maximum dose of crude oil. It also showed that chlorophyll content was decreased with increased concentration of crude oil. Results also demonstrated that there was a reduction in plant shoot and root biomass with the increase of crude oil concentration. Results also revealed that the shoot biomass is higher than root biomass. Morphology and anatomy of the experimental plant also show structural deformation in higher concentrations. Accumulation of crude oil on the cuticle of the transverse section of the leaves and shoot forms a thick dark layer. Estimation of the level of pollution in an environment due to oil spill is possible by the in-depth study of the harmful effects of oil on the morphology and anatomy and chlorophyll content of the plants grown in that particular environment.     

Adsorption of crude oil on arctic terrain

Arctic terrain was divided into three layers, moss, detritus and clay, and each layer was contacted with Norman Wells crude oil. Chromatographic analysis of the crude oil extracts of the terrain layers showed that the adsorption capacity of the terrain increased with increasing organic content. The higher molecular weight n-alkanes were adsorbed to a greater extent than lower n-alkanes on the moss and detritus layers. Of the aromatics, p-xylene was adsorbed to a greater extent than benzene on all three layers of the terrain. Retention of crude oil components on Arctic terrain in the event of an oil spill would be in accord with these findings.     

Efficiency of recycled wool-based nonwoven material for the removal of oils from water

The aim of this study was to highlight the potential use of recycled wool-based nonwoven material for the removal of diesel fuel, crude, base, vegetable and motor oil from water. Sorption capacity of the material in water and in oil without water, oil retention, sorbent reusability and buoyancy in static and dynamic conditions were investigated. The results show high sorption capacity of recycled wool for different kinds of oil. This sorbent also exhibited excellent buoyancy after 24h of sorption as well as a good reusability since the decrease in sorption capacity did not exceed 50% of the initial value after five sorption cycles in oil without water.     

Responses of juvenile sea bass, Dicentrarchus labrax, exposed to acute concentrations of crude oil, as assessed by molecular and physiological biomarkers

In the present study, juvenile sea bass were exposed for 48 and 96 h to an Arabian light crude oil and their responses were assessed at the molecular and physiological levels. The aim of the study was therefore to assess (i) the short term effects of crude oil exposure by the measurement of several molecular biomarkers, (ii) the consequences of this short term exposure on fish health by using growth and condition indices measured after a decontamination period of 28 and 26 d in seawater. Hydrocarbon petroleum concentrations was monitored during the 96 h experiments and an increase of PAH concentrations were found in fish following both exposure times. An 7-ethoxyresorufin-O-deethylase (EROD) induction was observed after 48 h of exposure, while a significant decrease in the sea bass specific growth rate in length and for the RNA:DNA ratio was observed 28 d after that exposure ceased. The EROD induction doubled after the 96 h exposure, and a significant increase in GST activities was observed. A significant decrease in the specific growth rates, the otolith recent growth, the RNA:DNA ratio and the Fulton’s K condition index were then observed in sea bass 26 d after the 96 h exposure to mechanically dispersed crude oil compared to the control. The present study shows that growth and condition indices can prove useful in assessing fish health status following an oil spill. Their complementary analysis with sensitive molecular biomarkers as EROD could improve the determination of oil spill impact on fish populations.     

秸秆固定化石油降解菌降解原油的初步研究

用秸秆做载体固定嗜碱芽孢杆菌(Bacillus alcalophilus SG)降解原油,其原油去除率为73.88%,高于单纯投加菌液或者菌液与秸秆的混合物的原油去除率.秸秆的最佳投加量(干重)为25.0 g/L,最佳固定化时间为30 h.用预处理过的秸秆固定SG,降低了固定化SG的原油去除率.在固定化培养基中添加无机盐离子,促进了固定化SG对原油的降解.不同初始pH的原油培养基在固定化SG降解原油的过程中逐渐呈中性或偏碱性.固定化SG在pH 6.0～10.0时对原油均有不错的降粘能力.     

Assessment of crude oil biodegradation in arctic seashore sediments: effects of temperature,salinity, and crude oil concentration

The expected increase in offshore oil exploration and production in the Arctic may lead to crude oil spills along arctic shorelines. To evaluate the potential effectiveness of bioremediation to treat such spills, oil spill bioremediation in arctic sediments was simulated in laboratory microcosms containing beach sediments from Barrow (Alaska), spiked with North Slope Crude, and incubated at varying temperatures and salinities. Biodegradation was measured via respiration rates (CO₂ production); volatilization was quantified by gas chromatography/mass spectrophotometry (GC/MS) analysis of hydrocarbons sorbed to activated carbon, and hydrocarbons remaining in the sediment were quantified by GC/flame ionization detector (FID). Higher temperature leads to increased biodegradation by naturally occurring microorganisms, while the release of volatile organic compounds was similar at both temperatures. Increased salinity had a small positive impact on crude oil removal. At higher crude oil dosages, volatilization increased, however CO₂ production did not. While only a small percentage of crude oil was completely biodegraded, a larger percentage was volatilized within 6–9 weeks.     

Influence of soil and hydrocarbon properties on the solvent extraction of high-concentration weathered petroleum from contaminated soils

Petroleum ether was used to extract petroleum hydrocarbons from soils collected from six oil fields with different history of exploratory and contamination. It was capable of fast removing 76–94 % of the total petroleum hydrocarbons including 25 alkanes (C₁₁–C₃₅) and 16 US EPA priority polycyclic aromatic hydrocarbons from soils at room temperature. The partial least squares analysis indicated that the solvent extraction efficiencies were positively correlated with soil organic matter, cation exchange capacity, moisture, pH, and sand content of soils, while negative effects were observed in the properties reflecting the molecular size (e.g., molecular weight and number of carbon atoms) and hydrophobicity (e.g., water solubility, octanol–water partition coefficient, soil organic carbon partition coefficient) of hydrocarbons. The high concentration of weathered crude oil at the order of 10⁵ mg kg^?1 in this study was demonstrated adverse for solvent extraction by providing an obvious nonaqueous phase liquid phase for hydrocarbon sinking and increasing the sequestration of soluble hydrocarbons in the insoluble oil fractions during weathering. A full picture of the mass distribution and transport mechanism of petroleum contaminants in soils will ultimately require a variety of studies to gain insights into the dynamic interactions between environmental indicator hydrocarbons and their host oil matrix.     

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。     

A comparison of the efficiency of different surfactants for removal of crude oil from contaminated soils

This paper presents the results from study investigating the efficiency with which different surfactants remove crude oil from contaminated soil using a soil washing process. The surfactants studied were aqueous solutions of rhamnolipid, saponin and sodium dodecyl sulfate (SDS). The efficiency of surfactants' removal was quantified and then GC/MS analysis conducted to investigate the distribution of hydrocarbons remaining on the washed soil samples compared to those on a control. The results showed that SDS removed the most crude oil from soil, followed by rhamnolipid and then saponin. However, the different surfactants showed preferences in terms of which crude oil components they removed from the contaminated soil. SDS removed more of the aliphatics than aromatic hydrocarbons whereas saponin removed the aromatic hydrocarbon preferentially to the aliphatic hydrocarbons. Clearly these results provide important information for the selection of surfactants used to remove crude oil from contaminated soils.     

Environmental photooxidation of dibenzothiophenes following the Amoco Cadiz oil spill

Photooxidation products of dibenzothiophenes (sulfur containing petroleum heteroaromatic hydrocarbons) were characterized in an oil slick sample obtained from a field location following the AMOCO CADIZ oil spill. The same oxidation products were formed in the laboratory by the photooxidation of a medium Arabian crude oil which contained the identical precursor hydrocarbons. Analytical techniques included fractionation by liquid/solid chromatography and characterization using high resolution gas chromatography-mass spectrometry. To the best of the author's knowledge, this represents the first reported instance for the formation of photooxidation products following an actual oil spill. A comparison of the quantities of various oxidation products was carried out by quantitative mass spectrometry using extracted ion current profiles of dibenzothiophenes and their corresponding sulfoxides. The geochemical and physiological implications of such photooxidation processes are also discussed.     

14C-dimethoate residues in olive oil during oil processing

An olive tree was treated twice in the field with 14C-dimethoate (237.7 muCi, 2.4 g) and 14C residues were determined in the olive fruits at harvest. The fruits were crushed and pressed to extract the crude oil, then refined by neutralization, bleaching and deodorization. The crude oil contained 14.1% of the total 14C in the olive fruits. Neutralization resulted in a reduction of 14C by about 50% of the total 14C residues in oil. Bleaching and deodorization processes further reduced the 14C residues and the refined oil contained 31.6% (which corresponds to 4.4% of 14C residues of the total 14C in olive fruits) of the total 14C in the crude oil. Industrially extracted crude oil was fortified with 14C-dimethoate at 1.8 mg kg-1 (0.02 muCi) level and subjected to the same refining process. A sharp decrease in the amount of 14C was observed by neutralization and the amount of 14C remaining in the refined oil was about 7.3% of the total 14C in the crude fortified oil. The data suggest that the 14C residues in the aged and the fortified oil amples were not of the same nature. The terminal 14C residue in the refined oil obtained from the field experiment did not contain dimethoate and/or its oxon.