PAH Degradation Research Articles

Photooxidation of Polycyclic Aromatic Hydrocarbons over NaBiO3 under Visible Light Irradiation

The NaBiO3 samples (NaBiO3 · nH2O) used in photooxidation of polycyclic aromatic hydrocarbon were obtained through heating NaBiO3 · 2H2O. The samples were characterized by X-ray diffractometer and ultraviolet-visible spectrophotometer. The photooxidation of anthracene and Benz[a]anthracene over NaBiO3 · nH2O was investigated, respectively. The intermediates were analysed by gas chromatography-mass spectrometer. The results indicated that the prepared NaBiO3 samples showed considerable photooxidation activity and stability for PAHs degradation under visible light irradiation. The possible reaction pathways of the decomposition of the two polycyclic aromatic hydrocarbons were proposed.

Degradation of phenanthrene and pyrene in rhizosphere of grasses and legumes

Phytoremediation is an emerging technology for the remediation of organic soil pollutants such as phenanthrene and pyrene (polycyclic aromatic hydrocarbons, PAHs). The PAH degradation ability of four native Korean plant species ( Panicum bisulcatum, Echinogalus crus- galli, Astragalus membranaceus, and Aeschynomene indica) was compared in the greenhouse. During the 80-day experiment, soil samples were collected and analyzed periodically to determine the residual PAH content and microbial activity. More PAHs were dissipated in planted soil (i.e., with a rhizosphere) than in unplanted soil, and there were more obvious effects of plants on pyrene dissipation than on phenanthrene dissipation. After 80 days, >99 and 77–94% of phenanthrene and pyrene, respectively, had been degraded in planted soil, whereas 99% and 69% had been degraded in unplanted soil. This enhanced dissipation of PAHs in planted soils might be derived from increased microbial activity and plant-released enzymes. During the experimental period, a relatively large amount of phenolic compounds, high microbial activity, and high peroxidase activity were detected in planted soils.

Microbial consortium bioaugmentation of a polycyclic aromatic hydrocarbons contaminated soil

In this study we evaluated the capacity of a defined microbial consortium (five bacteria: Mycobacterium fortuitum, Bacillus cereus, Microbacterium sp., Gordonia polyisoprenivorans, Microbacteriaceae bacterium, Naphthalene-utilizing bacterium; and a fungus identified as Fusarium oxysporum) isolated from a PAHs contaminated landfarm site to degrade and mineralize different concentrations (0, 250, 500 and 1000 mg kg −1) of anthracene, phenanthrene and pyrene in soil. PAHs degradation and mineralization was evaluated by gas chromatography and respirometry, respectively. The microbial consortium degraded on average, 99%, 99% and 96% of the different concentrations of anthracene, phenanthrene and pyrene in the soil, in 70 days, respectively. This consortium mineralized 78%, on average, of the different concentrations of the 3 PAHs in soil after 70 days. Contrarily, the autochthonous soil microbial population showed no substantial mineralization of the PAHs. Bacterial and fungal isolates from the consortium, when inoculated separately to the soil, were less effective in anthracene mineralization compared to the consortium. This signifies synergistic promotion of PAHs mineralization by mixtures of the monoculture isolates (the microbial consortium).

Biodegradation of PAHs and PCBs in Soils and Sludges

Results from a multi-year, pilot-scale land treatment project for PAHs and PCBs biodegradation were evaluated. A mathematical model, capable of describing sorption, sequestration, and biodegradation in soil/water systems, is applied to interpret the efficacy of a sequential active–passive biotreatment process of organic chemicals on remediation sites. To account for the recalcitrance of PAHs and PCBs in soils and sludges during long-term biotreatment, this model comprises a kinetic equation for organic chemical intraparticle sequestration process. Model responses were verified by comparison to measurements of biodegradation of PAHs and PCBs in land treatment units; a favorable match was found between them. Model simulations were performed to predict on-going biodegradation behavior of PAHs and PCBs in land treatment units. Simulation results indicate that complete biostabilization will be achieved when the concentration of reversibly sorbed chemical (SRA) reduces to undetectable levels, with a certain amount of irreversibly sequestrated residual chemical (SIA) remaining within the soil particle solid phase. The residual fraction (SIA) tends to lose its original chemical and biological activity, and hence, is much less available, toxic, and mobile than the “free” compounds. Therefore, little or no PAHs and PCBs will leach from the treatment site and constitutes no threat to human health or the environment. Biotreatment of PAHs and PCBs can be terminated accordingly. Results from the pilot-scale testing data and model calculations also suggest that a significant fraction (10–30%) of high-molecular-weight PAHs and PCBs could be sequestrated and become unavailable for biodegradation. Bioavailability (large Kd, i.e., slow desorption rate) is the key factor limiting the PAHs degradation. However, both bioavailability and bioactivity (K in Monod kinetics, i.e., number of microbes, nutrients, and electron acceptor, etc.) regulate PCBs biodegradation. The sequential active–passive biotreatment can be a cost-effective approach for remediation of highly hydrophobic organic contaminants. The mathematical model proposed here would be useful in the design and operation of such organic chemical biodegradation processes on remediation sites.

Evaluation of biodiesel as bioremediation agent for the treatment of the shore affected by the heavy oil spill of the Prestige

The efficiency of different bioremediation products (nutrients, microorganisms and biodiesel) was tested using tiles located in both the supra-littoral and intertidal zones of a beach that was affected by the heavy oil spill of the Prestige. Neither nutrients nor microorganisms meant an improvement with respect to the natural processes. The addition of biodiesel improved the appearance of the treated tiles and apparently accelerated the degradation of the aliphatic and aromatic fractions of the residual fuel oil. Nevertheless, PAHs degradation was similar and very high in all the treatments (80–85% after 60 days). On the other hand, the evolution with time of the amount of vanadium was similar to that of 17α(H),21β(H)-hopane, so it was concluded that vanadium could also be used to estimate the extent of oil degradation in the field. These results also suggested that the residual fuel oil mineralization was very low throughout 1 year in all the treatments. Moreover, the increase of the oxygen content of the residual oil from around 1% till 4–8% indicated that the partial oxidation of hydrocarbons took place, and that the hydrocarbon oxidation products accumulated in the polar fractions. In general, the results pointed out that bioremediation techniques were not suitable for the recovery of shores affected by heavy oil spills.

Co-variations of bacterial composition and catabolic genes related to PAH degradation in a produced water treatment system consisting of successive anoxic and aerobic units

This paper reports on the investigation of concentration levels of PAHs, community structure, as well as the abundance of PAH-related catabolic genes including upper-pathway dioxygenase genes (nahAc and phnAc) and down-pathway catechol dioxygenase genes (C12O and C23O) in a successive anoxic and aerobic treatment of produced water from the Jidong Oilfield, China. 93% of total PAHs were removed, almost equally contributed by the anoxic and aerobic units. However, PAHs of more than 3 benzene rings remained almost unchanged. The signals for phnAc and C12O were undetectable in this biological system, whereas the existence of nahAc and C23O was confirmed in the system and the copies of the two genes in the aerobic tank were 2 or 3 orders higher than those in the influent water sample. The different behavior of C23O demonstrated that mineralization of PAHs might mainly occur in the aerobic unit. The existence of nahAc and C23O genes in the influent and the high similarity of genotype between the influent and the two sludge samples suggested that bacteria existing in the influent contributed to PAH removal and bacteria harboring PAH catabolic genes were enriched in the sludge.

Isolation and characterization of a gene cluster involved in PAH degradation in Mycobacterium sp. strain SNP11: Expression in Mycobacterium smegmatis mc 2155

Mycobacterium sp. strain SNP11 is able to grow with pyrene, fluoranthene, phenanthrene and fluorene the sole carbon and energy sources. A probe based on the previously described gene pdoA2, which encodes the α subunit of a PAH ring-hydroxylating dioxygenase in Mycobacterium sp. strain 6PY1 [S. Krivobok et al., Identification of pyrene-induced proteins in Mycobacterium sp. strain 6PY1: evidence for two ring-hydroxylating dioxygenases, J. Bacteriol. 185(13) (2003) 3828–3841], was used to isolate a 14 kb DNA fragment from strain SNP11. Twelve putative open reading frames (ORFs), divided into two groups by a promoter intergenic region, were detected in this DNA sequence. The first gene cluster, located upstream of the promoter region, showed low but significant deduced amino acid sequence homologies with enzymes involved in aromatic degradation. The second gene cluster, under control of the promoter, contained pdoA2 (designated phdA in this study) and several other ORFs with deduced amino acid sequences closely related to enzymes involved in the phenanthrene-degrading pathway of Nocardioides sp. strain KP7. Gene expression analysis in Mycobacterium smegmatis mc 2155 revealed broad substrate specificity of the ring-hydroxylating dioxygenase, since transformant cells containing phdAB strongly oxidized fluoranthene, phenanthrene, anthracene, fluorine and dibenzofuran. Laser desorption/ionization time-of-flight mass spectrometry (LDI-ToF MS) analyses of culture media after PAH degradation by M. smegmatis transformants also revealed that the second gene cluster, located downstream of the promoter, takes an active share in initial phenanthrene and anthracene degradation by allowing transformation of these two PAHs in aromatic ring-cleaved metabolites.

액상 PAHs의 자외선에너지와 초음파를 이용한 분해

PAHs are major pollutants that are widely distributed in soil and groundwater environment, so that may be regarded as carcinogens. We investigated the degradation kinetics of PAH in aqueous solution when low pressure UV energy and ultrasonic irradiation were applied. Phenanthrene and pyrene were used as model compounds. The degrees of degradation of these compounds with time were analyzed with a GC/MSD (SIM-mode). UV photolysis experiments showed that phenanthrene was reduced by 90 -67% at initial concentrations of 1 ppm to 8ppm whilst it decreased to 50% at 10 ppm. Under the same conditions pyrene was degraded up to about 75% at lower initial concentrations but the reduction efficiency dropped to a level of 34 to 29% at the higher concentrations above 8 ppm. The reaction orders for phenanthrene and pyrene were found to be zero-th and ca. -0.4th order, respectively, thus implying that the reported assumption of pseudo 1st order reaction for some PAHs would be no longer valid. PAH degradation was roughly proportional to the intensity of UV (number of lamps), exhibiting maximum 92.5% of the degradation efficiency. The solution pH was lowered to 4.4 from 6.4 during the experiments partially because the carbons decomposed by the energy reacted with oxygen radicals to produce carbon dioxides. Ultrasonic irradiation on phenanthrene solutions gave relatively poor results which matched to 50 to 70% of degradation efficiency even at 2 ppm of initial concentration. Phenanthrene was found to be degraded more efficiently than pyrene for the two energy sources. Ultrasound also followed the same reaction kinetics as UV energy on PAH degradation.

Ecotoxicological assessment of PAHs and their dead-end metabolites after degradation by Mycobacterium sp. strain SNP11

Mycobacterium sp. SNP11 has a high PAH biodegradation potential. In this paper, the toxicity of pyrene, fluoranthene, phenanthrene, and their dead-end metabolites, accumulated in the media after biodegradation by Mycobacterium sp. SNP11, were evaluated by a screening battery of acute, chronic, and genotoxic tests. According to the bioassays, performed on bacteria ( Vibrio fischeri, Salmonella typhimurium strains TA1535/pSK1002, TA97a, TA98, TA100), algae ( Pseudokirchneriella subcapitata), and crustaceans ( Daphnia magna, Ceriodaphnia dubia), total disappearance or a very significant reduction of the (geno)toxic potential was observed after PAH degradation by Mycobacterium sp. SNP11.

Culture-based and culture-independent assessment of the impact of mixed and single plant treatments on rhizosphere microbial communities in hydrocarbon contaminated flare-pit soil

Phytoremediation is a novel treatment option for weathered, hydrocarbon contaminated, flare-pit soil in prairie ecosystems. The remediation potential of six different naturalized prairie plants was assessed by examining their impact on the degradation potential of indigenous bacterial communities. Culture-based and culture-independent microbiological methods were used to determine if mixed plant treatments stimulate different microbial communities and catabolic genotypes in comparison to individual plant species that comprise the mix. DGGE analysis of PCR-amplified 16S rRNA genes revealed that alfalfa ( Medicago sativa) had a dominant effect on the structure of rhizosphere microbial communities in mixed plant treatments, stimulating relative increases in specific Bacteroidetes and Proteobacteria populations. Alfalfa and mixes containing alfalfa, while supporting 100 times more culturable PAH degraders than other treatments, exhibited only 10% TPH reduction, less than all planted treatments except perennial rye grass ( Lolium perenne). Total petroleum hydrocarbon (TPH) reduction was greatest in single-species grass treatments, with creeping red fescue ( Festuca rubra) reducing the TPH concentration by 50% after 4.5 months. Overall TPH reduction throughout the study was positively correlated ( p < 0.001 ) to culturable n-hexadecane degraders.

Trials of bioremediation on a beach affected by the heavy oil spill of the Prestige

The objective of this study was to assess the efficiency of several bioremediation products in accelerating the in situ biodegradation of the heavy fuel oil spill of the Prestige. Trials of bioremediation were conducted in sand, rocks and granite tiles on the beach of Sorrizo (A Coruña, NW Spain) that was polluted by the spill. Neither the added microorganisms nor the nutrients significantly enhanced the degradation rate of the fuel oil in rocks, granite tiles or sand. PAH degradation up to 80% was determined in sand and tiles. In tiles the oxygen content of the residual oil increased from 1.6% up to 8% in 90 days, which could be explained by the accumulation of products coming from the partial oxidation of the hydrocarbons. Eighteen months after the spill, the rocks of the beach were still coated by a black layer of weathered fuel oil. For this reason an oleophilic product, sunflower biodiesel was tested on a rock. The application of biodiesel accelerated the gradually clean-up of the polluted surface and could also accelerate the degradation of the residual oil.

Plant-accelerated dissipation of phenanthrene and pyrene from water in the presence of a nonionic-surfactant

Plant-accelerated dissipation of phenanthrene and pyrene in water in the presence of a nonionic-surfactant (Brij35) was studied. The mechanisms involved were evaluated, based on the investigation of plant uptake of these compounds from water with Brij35. The presence of ryegrass ( Lolium multiflorum Lam) clearly enhanced the dissipation of tested PAHs in water with 0–296 mg l −1 Brij35. The first-order rate constants ( K), calculated from the first-order kinetic models for these PAH degradation (all significant at P < 0.05, n = 8), of phenanthrene and pyrene in the presence of ryegrass were 16.7–50% and 47.1–108% larger than those of plant-free treatments, whereas half-lives ( T 1/2) of the former were 14.3–33.4% and 32.0–52.0% smaller than the latter, respectively. However, the promotion of PAH dissipation by ryegrass was found to significantly decrease with increasing Brij35 concentrations. In the range of 0–296 mg l −1, low concentrations (⩽74.0 mg l −1) of Brij35 generally enhanced plant uptake and accumulation of phenanthrene and pyrene, based on the observed plant concentrations and accumulated amounts of these chemicals from water. In contrast, Brij35 at relatively high concentrations (⩾148 mg l −1) markedly restricted plant uptake of these PAHs. Plant accumulation of phenanthrene and pyrene accounted for 6.21–35.0% and 7.66–24.3% of the dissipation enhancement of these compounds from planted versus unplanted water bodies. In addition, plant metabolism was speculated to be another major mechanism of plant-accelerated dissipation of these PAHs in water systems. Results obtained from this study provided some insight with regard to the feasibility of phytoremediation for PAH contaminated water bodies with coexisted contaminants of surfactants.

Remediation of Soil and Ground Water Contaminated with PAH using Heat and Fe(II)-EDTA Catalyzed Persulfate Oxidation

The feasibility of degrading 16 USEPA priority polycyclic aromatic (PAH) hydrocarbons (PAHs) with heat and Fe(II)-EDTA catalyzed persulfate oxidation was investigated in the laboratory. The experiments were conducted to determine the effects of temperature (i.e. 20 ∘C, 30 ∘C and 40 ∘ C) and iron-chelate levels (i.e., 250 mg/L-, 375 mg/L- and 500 mg/L-Fe(II)) on the degradation of dissolved PAHs in aqueous systems, using a series of amber glass jars as the reactors that were placed on a shaker inside an incubator for temperature control. Each experiment was run in duplicate and had two controls (i.e., no persulfate in systems). Samples were collected after a reaction period of 144 hrs and measured for PAHs, pH and sodium persulfate levels. The extent of degradation of PAHs was determined by comparing the data for samples with the controls.

Root Exudates Impact on Phenanthrene Availability

In order to improve and optimize phytoremediation of PAH we propose to focus on the rhizospheric processes controlling PAH degradation. In this paper the effect of root exudates on PAH availability is studied. Model organic compounds (malic acid, malonic acid and EDTA) representing root exudates have been tested for their effect on phenanthrene sorption on a reference non polluted agricultural soil material. Phenanthrene adsorption isotherms were first obtained with batch experiments. Results showed linear isotherms and phenanthrene sorption was enhanced as the concentration of organic compounds in the solution increased. Column leaching experiments were then used to simulate the effect of root exudation following the soil pollution. Inlet solutions containing the different organic acids used were flowed through the column containing the artificially polluted soil material. Elution curves showed that the phenanthrene was less easily eluted when the solution injected contained the organic acids. However, magnitude of the phenomena did not fit with adsorption constants obtained in batch experiments. Phenanthrene desorption appeared limited by sequestration but organic acids seemed able to partially disturb the soil material structure to limit the sequestration effect.

Use of an avoidance test for the assessment of microbial degradation of PAHs

An avoidance test using the soil springtail Folsomia candida was used to assess changes in contamination levels at low doses of PAHs following incubation with indigenous microflora. A soil from a former coke site was diluted to 1% in an unpolluted soil from the same site, which was used as a control, then both substrates were remoistened to 80% field capacity. The diluted soil was previously shown to be strongly repellent to F. candida, although not toxic. After 2-month incubation at 20 °C, the mixture lost its repellence capacity and became attractive to the test animal, while the global 16 PAHs content had decreased to a great extent (50%). PAH disappearance was linked to the occurrence of indigenous microbiota able to degrade hydrocarbons.

The effects of carbon substrates for PAHs degradation and microbial community structure changing in anaerobic sediments of Taihu Lake

The effects of carbon substrates for PAHs degradation and microbial community structure changing in anaerobic sediments of Taihu Lake

PAH dissipation in spiked soil: Impacts of bioavailability, microbial activity, and trees

While trees have demonstrated potential in phytoremediation of several organic contaminants, little is known regarding their ability to impact the common soil contaminant PAHs. Several species of native North American trees were planted in soil artificially contaminated with three PAHs. Plant biomass, PAH dissipation, and microbial mineralization were monitored over the course of one year and environmental conditions were allowed to follow typical seasonal patterns. PAH dissipation and mineralization were not affected by planting. Extensive and rapid loss of PAHs was observed and attributed to high bioavailability and microbial activity in all treatments. The rate of this loss may have masked any significant planting effects. Anthracene was found to be more recalcitrant than pyrene or phenanthrene. Parallel soil aging studies indicated that sequestration to soil components was minimal. Contrary to common inferences in literature, amendment with decaying fine roots inhibited PAH degradation by the soil microbial community. Seasonal variation in environmental factors and rhizosphere dynamics may have also reduced or negated the effect of planting and should be taken into account in future phytoremediation trials. The unique root traits of trees may pose a challenge to traditional thought regarding PAH dissipation in the rhizosphere of plants.

Integrated treatment of PAH contaminated soil by soil washing, ozonation and biological treatment

The aim of the study was to optimise three different treatment methods and to find out if the integration of soil washing, ozonation and biological treatment could be a feasible method for the remediation of aged oil contaminated with PAHs. Three different ozone doses and soil washing were studied in different pHs in order to assess their effect to the degradation and enhancement of biodegradability of PAH in the soil and water phase. Main target of the study was to find out a method with which the PAH concentrations could be decreased below the Finnish guideline level for total PAHs. In this case, the initial concentration of PAHs was 1200 mg kg −1 and therefore almost 85% degradation of PAHs was required. Any of the methods studied was not able to reach this target level alone, but by several combinations of the methods studied achieved 90% reduction of PAHs. The consumption of ozone was 5–10 times lower in the integrated treatments of soil washing, ozonation and biological treatment than without prewashing.

Biodegradation of bilge waste from Patagonia with an indigenous microbial community

Oily residues that are generated in normal ship operation are considered hazardous wastes. A biodegradation assay with autochthonous microbiota of Bilge Waste Oily Phase (BWOP) was performed in a bioreactor under controlled conditions. Petroleum, diesel oil, and PAH degraders were isolated from bilge wastes. These bacteria belong to the genus Pseudomonas and are closely related to Pseudomonas stutzeri as shown by 16S rDNA phylogenetic analysis. The indigenous microbial community of the bilge waste was capable of biodegrading the BWOP (1% v/v) with biodegradation efficiencies of 70% for hexane extractable material (HEM), 68% for total hydrocarbons (TH) and 90% for total aromatics hydrocarbons (TA) in 14 days. Solid phase microextraction (SPME) was successfully applied to evaluate hydrocarbon evaporation in a control experiment and demonstrated a mass balance closure of 88%. The SPME and biodegradation results give useful information to improve and scale up the process for BWOP treatment.

Linking Catabolism to Cyclodextrin Extractability: Determination of the Microbial Availability of PAHs in Soil

When assessing the potential of a contaminated site for bioremediation, it is desirable to know how much of the contaminant(s) is available for microbial degradation, thus allowing the likelihood of successful bioremediation to be predicted. The aims of this study were to investigate the degradation of PAHs in two soils by a catabolic inoculum and indigenous soil microflora and link this to the cyclodextrin extractable fraction in the presence of transformer oil (0.05, 0.01, or 0.005%). This study showed very little difference between indigenous and inoculum-derived degradation for phenanthrene in laboratory-aged soil, and strong relationships were also observed between both of the microbial degradative conditions and the amount of phenanthrene extracted by cyclodextrin. Furthermore, the indigenous degradation of PAHs in a field-contaminated soil showed significant linear correlations with the cyclodextrin extractable fraction, with gradients approximating to 1. There are several novel facets to this study. First, in aged, contaminated soils, indigenous microflora gave an equally sensitive determination of degradative availability as that measured by the catabolic inoculum. Second, this is the first time intrinsic biodegradation of PAHs has been predicted by the cyclodextrin extraction in laboratory-spiked and field-contaminated soils. The cyclodextrin extraction technique represents a powerful tool for predicting the extent of intrinsic and augmented microbial degradation and will be useful in the assessment of contaminated land prior to bioremediation.