Pyrolysis-GC-MS analysis of crude and heavy fuel oil asphaltenes for application in oil fingerprinting

A Pyrolysis – Gas Chromatography – Mass Spectrometry (Py-GC-MS) method was developed for the analysis and profiling of crude and heavy fuel oil asphaltenes, for application in oil fingerprinting. Asphaltenes were precipitated from ten geographically different oils using n-pentane, and analysed by Py-GC-MS. Alkane profiles and sulphur/aromatic profiles were used to compare the oils, and to correctly differentiate oils from different geographical regions. Py-GC-MS could not differentiate a weathered oil sample and a fresh oil sample from the same source. The results of this study support the findings from a previously developed FTIR method for asphaltene profiling.     

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.     

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.     

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.     

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。     

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.     

Anti-oxidative property of crude rice oil extracted from cadmium-contaminated rice

Local residents who habitually consume cadmium-contaminated rice (Oryza sativa L.) can be exposed to cadmium toxicity in Mae Sot District, Tak Province, Thailand. This study aimed to investigate an alternative for utilizing cadmium-contaminated rice without compromising their health with hazard risks. First, cadmium (Cd) concentration in rice grain and crude rice oil was determined (0.203 ± 0.030 and 0.007 ± 0.002 mgCd/kg dry weight, respectively). Then crude rice oil extracted from cadmium-contaminated rice grain was studied for its anti-oxidative property using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging approach. Next, quantitative analysis of γ-oryzanol in crude rice oil was conducted. Results indicated that the level of cadmium concentration in the rice grain could cause adverse effects on human health. However, the amount of cadmium in the crude rice oil was safe for consumption. In crude rice oil anti-oxidative property, crude rice oil extracted from cadmium-contaminated rice was significantly higher than the control (P < 0.05). The concentration of γ-oryzanol in crude rice oil extracted from cadmium-contaminated rice was significantly higher than that in the control crude rice oil (P < 0.05). This study demonstrates an alternative way to use the rice grown in cadmium-contaminated areas for crude rice oil production for its anti-oxidative properties.     

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.     

生物柴油促进原油污染砂粒释放油

对4种生物柴油促进原油污染砂粒释放油的效果进行了研究,并探讨了菜籽生物柴油投加量和砂粒粒径对促进效果的影响。结果表明,菜籽生物柴油的促进效果最好,8 h释放量达到73%,废油脂生物柴油的效果最差,仅为52%;生物柴油的促进效果随着投加量的增大而升高,当投加量超过海水体积的5%时促进效果不再明显增加;在生物柴油作用下,小粒径砂粒上原油的释放效果优于大粒径砂粒。     

Detailed characterization of polar compounds of residual oil in contaminated soil revealed by Fourier transform ion cyclotron resonance mass spectrometry

Effects of remediation technologies on polar compounds of crude oil in contaminated soils have not been well understood when compared to hydrocarbons. In this study, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the changes in NSO polar compounds of crude oil and residual oil after long-term natural attenuation, biostimulation and subsequent ozonation following biostimulation of contaminated soils. N₁ and O₁ species, which were abundant in the crude oil, were selectively biodegraded, and species with higher double bond equivalent values and smaller carbon numbers appeared to be more resistant to microbial alteration. O₂-O₆ species were enriched by biodegradation and contained a large number of compounds with a high degree of unsaturation. Ozone could react with a variety of polar compounds in residual oil after biodegradation and showed high reactivity with polar species containing aromatic or multi-aliphatic rings, including the residual N₁ and O₁ species, naphthenic acids and unsaturated O₃-O₆ compounds. Fatty acids and O₃-O₈ species dominated by saturated alkyl compounds were resistant to ozonation or the primarily incomplete ozonation products. Principal component analysis of identified peaks in the FT-ICR MS spectra provided a comprehensive overview of the complex samples at the molecular level and the results were consistent with the detailed analysis. Taken together, these results showed the high complexity of polar compounds in residual oils after biodegradation or ozonation in contaminated soil and would contribute to a better understanding of bioremediation and ozonation processes.     

High-molecular weight sulfur-containing aromatics refractory to weathering as determined by Fourier transform ion cyclotron resonance mass spectrometry

Biomarkers and low-molecular weight polyaromatic compounds have been extensively studied for their fate in the environment. They are used for oil spill source identification and monitoring of weathering and degradation processes. However, in some cases, the absence or presence of very low concentration of such components restricts the access of information to spill source. Here we followed the resistance of high-molecular weight sulfur-containing aromatics to the simulated weathering condition of North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The sulfur aromatics in North Sea crude having double bond equivalents (DBE) from 6 to 14 with a mass range 188-674 Da were less influenced even after 6 months artificial weathering. Moreover, the ratio of dibenzothiophenes (DBE 9)/naphthenodibenzothiophenes (DBE 10) was 1.30 and 1.36 in crude oil and 6 months weathered sample, respectively reflecting its weathering stability. It also showed some differences within other oils. Hence, this ratio can be used as a marker of the studied crude and accordingly may be applied for spilled oil source identification in such instances where the light components have already been lost due to environmental influences.     

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.     

Evaluation of biosurfactants for crude oil contaminated soil washing

An evaluation of the ability of aqueous biosurfactant solutions (aescin, lecithin, rhamnolipid, saponin and tannin) for possible applications in washing crude oil contaminated soil was carried out. The biosurfactants behaviour in soil-water, water-oil and oil-soil systems (such as foaming, solubilization, sorption to soil, emulsification, surface and interfacial tension) was measured and compared with a well-known chemical surfactant (sodium dodecyl sulphate, SDS) at varying concentrations. Results showed that the biosurfactants were able to remove significant amount of crude oil from the contaminated soil at different solution concentrations for instance rhamnolipid and SDS removed up to 80% oil and lecithin about 42%. The performance of water alone in crude oil removal was equally as good as those of the other biosurfactants. Oil removal was due to mobilization, caused by the reduction of surface and interfacial tensions. Solubilization and emulsification effects in oil removal were negligible due to the low crude oil solubilization of 0.11%. Therefore, these studies suggest that knowledge of surfactants' behaviour across different systems is paramount before their use in the practical application of oil removal.     

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.     

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.     

14C‐dimethoate residues in olive oil during oil processing

Abstract

An olive tree was treated twice in the field with ¹⁴C‐dimethoate (237.7 (μCi, 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 ^I4C 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 μCi) 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 ^l4C 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.     

Soil contamination by crude oil: impact on the mycorrhizosphere and on the revegetation potential of forest trees

In vitro and greenhouse biotests were carried out to study the effects of various concentrations of crude oil on the mycorrhizosphere and the ability of ectomycorrhizal fungi to colonise Norway spruce and poplar seedlings grown on contaminated soil. Ectomycorrhizal fungi grown in pure cultures showed a variety of reactions to crude oil, ranging from growth stimulation to total inhibition of growth, depending on the species of fungi. Germination of poplar and spruce seeds was not significantly affected. The growth of spruce seedlings was not affected by crude oil, whereas that of poplar seedlings was significantly reduced at high concentrations. None of the concentrations had any effect on the degree of ectomycorrhizal and endomycorrhizal colonisation of poplar. With spruce, however, the ectomycorrhizal fungi showed species-specific reactions to increasing concentrations, in accordance with the results of the pure culture test. The length of time between soil contamination and seeding affects both seedling growth and the mycorrhizal infection potential of the soil. The results confirm the importance of mycorrhizal fungi in the bioremediation of soils contaminated by crude 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.     

润滑油废白土的热解处理

以润滑油废白土为原料,利用电热解法,研究了热解终温、加热速率和CaO添加量对热解产物的影响。实验结果表明:热解终温对热解产物的影响最为显著。随着热解终温的升高,不凝气产量和产油率均迅速增加。当热解终温达到600℃时,其增加的速率逐渐缓慢增大。当控制热解终温为800℃、加热速率为16℃/min、CaO添加量为0.5%时,富氢气体产量为189.2 L/kg,气体中主要成分为H2和CH4,其含量分别为27.97%和41.64%;热解残渣含油率和重金属溶出物均低于标准规定值,热解油产率为10.98%,回收率为38.94%,其主要成分为汽油、柴油和重油3部分组成,分别含19.13%、31.35%和49.52%。     

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.