Polycyclic Aromatic Hydrocarbons In Crude Oil Research Articles

Bioremediation of polycyclic aromatic hydrocarbons in crude oil by bacterial consortium in soil amended with Eisenia fetida and rhamnolipid.

The present study investigated the concerted effort of Eisenia fetida and rhamnolipid JBR-425 in combination with a five-member bacterial consortium exhibiting elevated degradation levels of low and high molecular weight polycyclic aromatic hydrocarbons (PAH) from soil contaminated with Digboi crude oil. Application of bacterial consortium (G2) degraded 30-89% of selected PAH from the artificial soil after a 45-day post-exposure, in which chrysene showed the highest level of degradation with 89% and benzo(a)pyrene is the lowest with 30%, respectively. Moreover, an acute exposure study observed that earthworm biomass decreased, and mortality rates increased with increasing crude oil concentrations (0.25 to 2%). Earthworms with a 100% survival rate at 1% crude oil exposure suggest the tolerance potential and its mutual involvement in the bioremediation of crude oil with selected bacterial consortia. Bacterial consortium assisted with E. fetida (G3) showed 98% chrysene degradation with a slight change in benzo(a)pyrene degradation (35%) in crude oil spiked soil. Besides, the most dominant PAH in crude oil found in the current work, fluoranthene, undergoes 93% and 70% degradation in G3 and G5 groups, respectively. However, rhamnolipid JBR-425 coupled with the bacterial consortium (G5) has resulted in 97% degradation of chrysene and 33% for benzo(a)pyrene. Overall, bacterial consortium assisted with earthworm group has shown better degradation of selected PAH than bacterial consortium with biosurfactant. Catalase (CAT), glutathione reductase (GST) activity and MDA content was found to be reduced in earthworms after sub-lethal exposure, suggesting oxidative stress prevalence via reactive oxygen species (ROS). Hence, the findings of the present work suggest that the application of a bacterial consortium, along with earthworm E. fetida, has huge potential for field restoration of contaminated soil with PAH and ecosystem sustainability.

Anaerobic degradation of high-concentration polycyclic aromatic hydrocarbons (PAHs) in seawater sediments

Recurring oil spill accidents have been a global challenge and contribute to PAHs' heavy accumulation in marine sediments. The rapid bioremediation of PAHs with high concentrations in marine sediments has rarely been studied. In this study, four representative PAHs in crude oil were tested for fast anaerobic biodegradation. An efficient system for the anaerobic degradation of high-concentration PAHs was obtained using petroleum-acclimated marine sediments as inoculants in the treatment system. The degradation efficiencies of benzo[b]fluoranthene, benzo[a]pyrene, pyrene, and phenanthrene reached 0.21, 1.71, 3.89, and 4.10 mg/(L·d), respectively, which are 16, 2.8, 1.8, and 1.0 times higher than the reported values. Nitrate was preferred to sulfate as an electron acceptor. The acclimated sediment contains a high abundance of hydrocarbon-degrading bacteria. The number and diversity of species in the treatment system supplemented with PAHs decreased, but the abundance of some hydrocarbon-degrading bacteria and hydrocarbon-intermediate utilising bacteria increased, and ecological succession was observed.

Physiological responses and phytoremediation capability of Avicennia marina to oil contamination

The impact of oil pollution on coastal vulnerable ecosystems has been a major concern especially, in the Persian Gulf area. The current study was carried out to assess to what extent Avicennia marina can tolerate oil contamination and degrade crude oil polycyclic aromatic hydrocarbons (PAHs) from rhizosphere soil. Seeds of A. marina were grown in control and crude oil-contaminated (2.5, 5.0, 7.5, and 10% w/w) soil under ambient greenhouse conditions. Four-month-old plants were collected, measured for their biometry, and assayed for physiological characteristics in relation to degradation of PAHs. A. marina exposed to petroleum responded by allocating proportionally more biomass to root than shoot, activating enzymatic and non-enzymatic antioxidative mechanisms and removing of PAHs, particularly in lower concentrations of crude oil in the soil. The content of total PAHs in A. marina rhizosphere soil, grown on 2.5, 5.0, 7.5 and 10% oil-treated soils were, respectively, 37 ± 0.4, 21.84 ± 0.27, 12.78 ± 0.11 and 14.74 ± 0.03% lower than non-rhizosphere soil. Comparison of PAHs content of rhizospheric and non-rhizospheric soil also indicated that the highest rate of PAH removal was for acenaphthene (74.63 ± 0.78) in control, fluoranthene (71.18 ± 0.56) in 2.5%, and anthracene (69.45 ± 6.33, 55.66 ± 4.38 and 35.97 ± 0.22) in 5.0, 7.5 and 10% oil-contaminated soil and acenaphthene (74.63 ± 0.78) in control. Activities of peroxidase, ascorbate peroxidase, and polyphenol oxidase were more prominent in the roots of plants exposed to increasing concentrations of oil in soil than control plants. Conversely, the activity of superoxide dismutase decreased. These findings render A. marina as a phytoremediation candidate for small scale oil spills and residual oil pollution in coastal marine environments.

Quantitative analysis of PAH compounds in DWH crude oil and their effects on Caenorhabditis elegans germ cell apoptosis, associated with CYP450s upregulation

The Deepwater Horizon (DWH) oil spill marked the largest environmental oil spill in human history, where it was estimated a large amount of the polycyclic aromatic hydrocarbons (PAHs) were released with crude oil into the environment. In this study, common PAH compounds were quantitatively determined in crude oil from the DWH spill by gas chromatography-mass spectroscopy (GC–MS). Twelve PAH compounds were identified and quantified from a 100× dilution of DWH crude oil: naphthalene (7800 ng/mL), acenaphthylene (590 ng/mL), acenaphtehen (540 ng/mL), fluorene (2550 ng/mL), phenanthrene (2910 ng/mL), anthracene (840 ng/mL), fluoranthene (490 ng/mL), pyrene (290 ng/mL), benzo(k) fluoranthene (1050 ng/mL), benzo(b)fluoranthene (1360 ng/mL), dibenz(a,h)anthracene (2560 ng/mL), and benzo(g, h, i) perylene (630 ng/mL). Toxicity assays using the nematode, Caenorhabditis elegans (C. elegans), indicated a single PAH compound naphthalene, exposure increased C. elegans germ cell apoptosis which may adversely affect progeny reproduction. The number of apoptotic germ cells significantly increased from 1.4 to 2.5 when worms were treated with 10 μg/mL of naphthalene and from 1.3 to 2.5 and 3.5 cells in presence of 1 μg/mL and 5 μg/mL of benzo(a)pyrene, respectively. Five CYP450 genes (CYP14A3, CYP35A1, CYP35A2, CYP35A5, and CYP35C1) were significantly upregulated following 500× dilution of dispersed crude oil exposure (p < 0.05). These results suggest that CYP450s may play a role in bioactivation of PAHs in crude oil, resulting in DNA damage related germ cell apoptosis.

Risk assessment of Arctic aquatic species using ecotoxicological biomarkers and Bayesian network

The risk to Arctic aquatic species due to accidental oil spills is not well studied. One of the key reasons for this limitation is the lack of understanding of the dose-response relations for the species in the Arctic region. The present study addresses this knowledge gap. It proposes a new approach to develop dose-response curves for Arctic aquatic species. The application of the approach is demonstrated using the estimation of mortality risk in Boreogadus saida (polar cod) due to exposure from polycyclic aromatic hydrocarbons (PAH).The proposed approach considers the toxicity mechanism in Arctic species (i.e. polar cod) and regional environmental factors, and models these as a belief-based Bayesian Network (BN). The BN model integrates diverse ecotoxicology biomarker data types and predicts the cell death probability due to exposure to a toxicant (PAH in crude oil). The input data and results from the model were verified using data available in the literature. Seasonal sea ice played a major role in containing PAH exposure and subsequent risk to polar cod. However, the physiological factors, such as presence of higher Phase II activity, and higher oxyradical scavenging ability, had greater impact on PAH risk mitigation.

Biodegradation of polycyclic aromatic hydrocarbons in crude oil-contaminated soil using composted market waste

Release of crude oil and its products into the environment has resulted in many problems that are of global concern. The objective of this study was to determine effect of Composted Market Waste (CMW) on the degradation of Polycyclic Aromatic Hydrocarbons (PAHs) in crude oil-contaminated soil. Pot experiment was carried out with 1 kg of soil in 7 litres perforated container contaminated with 10 % w/ w crude oil, followed by amendment with CMW at 0, 350 and 450 g. The soil was analysed for PAH after 21 days using GC-FID. Acenaphthylene, Acenaphthene, Phenanthrene, Benzo (g,h,i) perylene, Indeno (1,2,3-cd) perylene, Pyrene and Benzo (b) fluoranthene were present in the crude oil-contaminated soil. Concentrations of PAHs at the end of the experiment were 188.40, 38.45 and 32.73 ppm in control, 350 and 450 g respectively. Composted market waste enhanced degradation of PAHs in crude oil- contaminated soil. Keywords: PAH, Degradation, Crude oil, Compost

Developmental toxicity of hydroxylated chrysene metabolites in zebrafish embryos

One of the primary sources of polycyclic aromatic hydrocarbons (PAHs) in marine environments is oil. Photochemical oxidation and microbial transformation of PAH-containing oils can result in the formation of oxygenated products. Among the PAHs in crude oil, chrysene is one of the most persistent within the water column and may be transformed to 2- and 6-hydroxychrysene (OHCHR). Both of these compounds have been shown to activate (2-OHCHR) and antagonize (6-OHCHR) the estrogen receptor (ER). Previous studies in our lab have shown that estrogen can significantly alter zebrafish development. However, little is known about the developmental toxicity of hydroxylated PAHs. Zebrafish embryos were exposed to 0.5–10μM of 2- or 6-OHCHR from 2h post-fertilization (hpf) until 76hpf. A significant decrease in survival was observed following exposure to 6-OHCHR – but not 2-OHCHR. Both OHCHRs significantly increased the percentage of overall deformities after treatment. In addition to cardiac malformations, ocular and circulatory defects were also observed in embryos exposed to both compounds, while 2-OHCHR generally resulted in a higher prevalence of effect. Moreover, treatment with 2-OHCHR resulted in a significant decrease in hemoglobin levels. ER nor G-Protein coupled estrogen receptor (GPER) antagonists and agonists did not rescue the observed defects. We also analyzed the expression of cardiac-, eye- and circulation-related genes previously shown to be affected by oil. Rhodopsin mRNA expresssion was significantly decreased by both compounds equally. However, exposure to 2-OHCHR significantly increased the expression of the hematopoietic regulator, runx1 (runt related transcription factor 1). These results indicate the toxicity of oxygenated photoproducts of PAHs and suggest that other targets and signaling pathways may contribute to developmental toxicity of weathered oil. Our findings also demonstrate the regio-selective toxicity of hydroxy-PAHs in the effects on eye and circulatory development and raise the need to identify mechanisms and ecological risks of oxy-PAHs to fish populations.

Sustained impairment of respiratory function and swim performance following acute oil exposure in a coastal marine fish

Acute exposure to crude oil polycyclic aromatic hydrocarbons (PAH) can severely impair cardiorespiratory function and swim performance of larval fish; however, the effects of acute oil exposure on later life stages and the capacity for subsequent recovery is less clear. Red drum (Sciaenops ocellatus) is an economically important apex predator native to the Gulf of Mexico, which was directly exposed to the 2010 Deep Water Horizon (DWH) oil spill. Here we examine impact and recovery of young adult red drum from exposure to concentrations of 0, 4.1, and 12.1μgL−1 ΣPAH50 naturally weathered oil-water accommodated fractions (geometric mean), which are well within the range of concentrations measured during the DWH incident. We focused on aerobic scope (ASc), burst- and critical swimming speeds (Uburst and Ucrit), cost of transport (COT), as well as the capacity to repay oxygen debt following exhaustive exercise (EPOC), which are critical parameters for success of all life stages of fishes. A 24h acute exposure to 4.1μgL−1 ΣPAH caused a significant 9.7 and 12.6% reduction of Uburst and Ucrit respectively, but no change in ASc, COT or EPOC, highlighting a decoupled effect on the respiratory and swimming systems. A higher exposure concentration, 12.1μgL−1 ΣPAH, caused an 8.6 and 8.4% impairment of Uburst and Ucrit, as well as an 18.4% reduction in ASc. These impairments persisted six weeks post-exposure, suggesting that recorded impacts are entrenched. Large predatory fishes are critically dependent on the cardiorespiratory and swimming systems for ecological fitness, and long-term impairment of performance due to acute oil exposure suggests that even acute exposure events may have long lasting impacts on the ecological fitness of affected populations.

Crude oil polycyclic aromatic hydrocarbons removal via clay-microbe-oil interactions: Effect of acid activated clay minerals

Acid treatment of clay minerals is known to modify their properties such as increase their surface area and surface acidity, making them suitable as catalysts in many chemical processes. However, the role of these surface properties during biodegradation processes of polycyclic aromatic hydrocarbons (PAHs) is only known for mild acid (0.5 M Hydrochloric acid) treated clays. Four different clay minerals were used for this study: a montmorillonite, a saponite, a palygorskite and a kaolinite. They were treated with 3 M hydrochloric acid to produce acid activated clay minerals. The role of the acid activated montmorillonite, saponite, palygorskite and kaolinite in comparison with the unmodified clay minerals in the removal of PAHs during biodegradation was investigated in microcosm experiments. The microcosm experiments contained micro-organisms, oil, and clays in aqueous medium with a hydrocarbon degrading microorganism community predominantly composed of Alcanivorax spp. Obtained results indicated that acid activated clays and unmodified kaolinite did not enhance the biodegradation of the PAHs whereas unmodified montmorillonite, palygorskite and saponite enhanced their biodegradation. In addition, unmodified palygorskite adsorbed the PAHs significantly due to its unique channel structure.

Removal Capacities of Polycyclic Aromatic Hydrocarbons (PAHs) by a Newly Isolated Strain from Oilfield Produced Water.

The polycyclic aromatic hydrocarbon (PAH)-degrading strain Q8 was isolated from oilfield produced water. According to the analysis of a biochemical test, 16S rRNA gene, house-keeping genes and DNA–DNA hybridization, strain Q8 was assigned to a novel species of the genus Gordonia. The strain could not only grow in mineral salt medium (MM) and utilize naphthalene and pyrene as its sole carbon source, but also degraded mixed naphthalene, phenanthrene, anthracene and pyrene. The degradation ratio of these four PAHs reached 100%, 95.4%, 73.8% and 53.4% respectively after being degraded by Q8 for seven days. A comparative experiment found that the PAHs degradation efficiency of Q8 is higher than that of Gordonia alkaliphila and Gordonia paraffinivorans, which have the capacities to remove PAHs. Fourier transform infrared spectra, saturate, aromatic, resin and asphaltene (SARA) and gas chromatography–mass spectrometry (GC–MS) analysis of crude oil degraded by Q8 were also studied. The results showed that Q8 could utilize n-alkanes and PAHs in crude oil. The relative proportions of the naphthalene series, phenanthrene series, thiophene series, fluorene series, chrysene series, C21-triaromatic steroid, pyrene, and benz(a)pyrene were reduced after being degraded by Q8. Gordonia sp. nov. Q8 had the capacity to remediate water and soil environments contaminated by PAHs or crude oil, and provided a feasible way for the bioremediation of PAHs and oil pollution.

Removal of crude oil polycyclic aromatic hydrocarbons via organoclay-microbe-oil interactions

Clay minerals are quite vital in biogeochemical processes but the effect of organo-clays in the microbial degradation of crude oil polycyclic aromatic hydrocarbons is not well understood. The role of organo-saponite and organo-montmorillonite in comparison with the unmodified clays in crude oil polycyclic aromatic hydrocarbons (PAHs) removal via adsorption and biodegradation was studied by carrying out microcosm experiments in aqueous clay/oil systems with a hydrocarbon degrading microbial community that is predominantly alcanivorax spp. Montmorillonite and saponite samples were treated with didecyldimethylammonium bromide to produce organo-montmorillonite and organo-saponite used in this study. Obtained results indicate that clays with high cation exchange capacity (CEC) such as montmorillonite produced organo-clay (organomontmorillonite) that was not stimulatory to biodegradation of crude oil polycyclic aromatic compounds, especially the low molecular weight (LMW) ones, such as dimethylnaphthalenes. It is suggested that interaction between the organic phase of the organo-clay and the crude oil PAHs which is hydrophobic in nature must have reduced the availability of the polycyclic aromatic hydrocarbons for biodegradation. Organo-saponite did not enhance the microbial degradation of dimethylnaphthalenes but enhanced the biodegradation of some other PAHs such as phenanthrene. The unmodified montmorillonite enhanced the microbial degradation of the PAHs and is most likely to have done so as a result of its high surface area that allows the accumulation of microbes and nutrients enhancing their contact.

Effects of Neutralization, Decoloration, and Deodorization on Polycyclic Aromatic Hydrocarbons during Laboratory-Scale Oil Refining Process

The influence of technological operations during oil refining process on polycyclic aromatic hydrocarbons (PAHs) in neutralized, bleached, and deodorized oils was investigated on the basis of laboratory-scale study. Under the best experimental conditions, benzo[a]pyrene decreased by 85.1%, 99.7%, and 40.8% in neutralized, bleached, and deodorized oils, respectively. Total of 16 analytes decreased by 55.7%, 87.5%, and 47.7%, respectively. Bleaching with activated charcoal was the most efficient procedure to reduce PAHs in crude oil. Neutralization had a modest influence on sixteen analytes; however, deodorization was only responsible for a slight decrease in the light PAHs and heavy PAHs contents. Data obtained in this study suggest that the use of activated carbon during oil refining process is highly recommended; moreover, these results provide a useful guidance for oil refining plant to reduce security risk and ensure the quality of the vegetable oil products.

Determination of volatile organic and polycyclic aromatic hydrocarbons in crude oil with efficient gas-chromatographic methods.

Determination of volatile organic compounds (VOCs) in crude oil, such as super volatile organic compounds (super VOCs) and simple polycyclic aromatic hydrocarbons (PAHs), is vital for targeting crude oil spill spots. In this study, a static headspace gas chromatography flame ionization detection method was established for determination of super VOCs in crude oil with both external and internal standard determination, which can be used in the field when using portable gas chromatography. Identification was done by comparing the retention time with the corresponding standards and quantitation was done with a new one-drop method. Another simplified and efficient method was performed to analyze volatile PAHs in crude oil, which can also be used in field analysis. Toluene was used as the extraction solvent for PAHs in crude oil. Method validation for both analyses was satisfactory. The result showed that n-butane and n-pentane were maximum super VOCs and naphthalene, phenanthrene and fluorene were the main PAHs in the crude oil studied. The super VOCs quantity ranged from 3 to 6% and the main PAHs consisted of 0.02-0.06% of studied crude oil.

Dispersant and salinity effects on weathering and acute toxicity of South Louisiana crude oil

Chemical dispersants are an important technology in the remediation of oil spills in the aquatic environment, facilitating degradation of crude oil and salinity is an important factor in dispersant effectiveness. The aim of the present study was to explore the role of salinity on the degradation chemistry of crude oil polycyclic aromatic hydrocarbons (PAHs) and acute toxicity of the water accommodated fraction (WAF) of the dispersant COREXIT 9500A and chemically dispersed crude oil on a common estuarine fish. Laboratory microcosms were designed at salinities of 4 parts per thousand (ppt), 12 ppt, or 18 ppt and spiked with crude oil, COREXIT 9500A, or a combined exposure to crude oil and COREXIT and allowed to biodegrade for 1 wk, 4 wk, and 16 wk. The WAF was harvested for analytical PAH analysis and acute toxicity testing in juvenile Fundulus grandis. Compared with undispersed oil, COREXIT exponentially increased the PAH concentrations in the WAF for up to 16 wk; hopane-normalized concentrations indicated that biodegradation was slowed for the first 4 wk. Dispersed crude oil and COREXIT were acutely toxic following 1 wk of biodegradation with no correlation between PAH concentrations and crude oil WAF mortality. Both dispersant and dispersant oil mixtures remained toxic for at least 4 wk at the lowest salinity tested, suggesting increased sensitivity or reduced biodegradation of toxic components in low-saline environments. At the lowest salinity, oil dispersed with COREXIT was more toxic than either the COREXIT alone or oil alone, even after 16 wk of biodegradation.

Partitioning of crude oil polycyclic aromatic hydrocarbons in aquatic systems.

This paper investigates the hypothesis that observed polycyclic aromatic hydrocarbon (PAH) concentrations in an aqueous system are equal to the sum of the organic phase and soluble phase molar concentrations. While the organic phase concentrations are proportional to the PAH mole fraction in the oil, the soluble phase molar concentrations are estimated using Raoult's law. A batch laboratory mixing vessel with a scalable mixing energy was loaded initially at various oil layer thicknesses (0.4-3.2 mm) which correspond to oil surface loadings (40-310 mg/cm2). The vessel was agitated at constant mean shear rates (Gm = 5, 20 s(-1)). Total petroleum hydrocarbon (TPH) samples were taken periodically to estimate the entrainment rate as a function of initial oil layer thickness. TPH concentrations were measured in-situ using a laser scattering instrument (LISST-100) and ex-situ using gravimetric analysis. At a steady-state TPH concentration (>72 h), additional samples were analyzed for PAH concentration using GC/MS analysis. TPH concentrations increased over time according to a first-order kinetic model. Generally, the first-order rate constant and steady-state concentration both increased with increased oil loading and with increased Gm. In addition, measured PAH concentrations correlated well (r2 > 0.96) with those predicted by a partitioning model. These results are useful for assessing the effects of mixing and oil loading conditions on crude oil entrainment and PAH partitioning.