Polycyclic aromatic hydrocarbon and n-alkane pollution characteristics and structural and functional perturbations to the microbial community: a case-study of historically petroleum-contaminated soil

Characterization of the typical petroleum pollutants, polycyclic aromatic hydrocarbons (PAHs) and n-alkanes, and indigenous microbial community structure and function in historically contaminated soil at petrol stations is critical. Five soil samples were collected from a petrol station in Beijing, China. The concentrations of 16 PAHs and 31 n-alkanes were measured by gas chromatography-mass spectrometry. The total concentrations of PAHs and n-alkanes ranged from 973 ± 55 to 2667 ± 183 μg/kg and 6.40 ± 0.38 to 8.65 ± 0.59 mg/kg (dry weight), respectively, which increased with depth. According to the observed molecular indices, PAHs and n-alkanes originated mostly from petroleum-related sources. The levels of ΣPAHs and the total toxic benzo[a]pyrene equivalent (ranging from 6.41 to 72.54 μg/kg) might exert adverse biological effects. Shotgun metagenomic sequencing was employed to investigate the indigenous microbial community structure and function. The results revealed that Proteobacteria and Actinobacteria were the most abundant phyla, and Nocardioides and Microbacterium were the important genera. Based on COG and KEGG annotations, the highly abundant functional classes were identified, and these functions were involved in allowing microorganisms to adapt to the pressure from contaminants. Five petroleum hydrocarbon degradation-related genes were annotated, revealing the distribution of degrading microorganisms. This work facilitates the understanding of the composition, source, and potential ecological impacts of residual PAHs and n-alkanes in historically contaminated soil.

     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

Distribution of polycyclic aromatic hydrocarbons in thirty typical soil profiles in the Yangtze River Delta region, east China

Polycyclic aromatic hydrocarbons (PAHs) were quantified in 30 soil profiles from the Yangtze River Delta Region, in east China. Relative concentrations of PAH compounds with different benzene rings and ratios of fluoranthene to fluoranthene plus pyrene and benz(a)anthracene to benz(a)anthracene plus chrysene were used to identify the possible sources of soil PAHs. Total concentrations of 15 PAHs in topsoils ranged from 8.6 to 3881 microg kg(-1) with an average of 397 microg kg(-1). Half of the soil samples were considered to be contaminated with PAHs (>200 microg kg(-1)) and two sampling sites were heavily polluted by PAHs with concentrations >1000 microg kg(-1). Phenanthrene was found in soils below a depth of 100 cm in half of the sampling sites, but the detectable ratio of benzo(a)pyrene decreased sharply from 100% in topsoil to 0 in the 4th horizon.     

Petroleum hydrocarbons and polycyclic aromatic hydrocarbons in the surficial sediments of Xiamen Harbour and Yuan Dan Lake, China

Surficial sediments were sampled from nine stations in Xiamen Harbour and two stations in Yuan Dan Lake during April 2002. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Selected ion monitoring was at M/Z=57 for petroleum hydrocarbons (PHCs) and individual M/Zs for each of the 15 typical polycyclic aromatic hydrocarbons (PAHs) and nine alkylated PAHs. The results showed that concentrations of PHCs and total PAHs in the sediments of Yuan Dan Lake were 1397 microg g(-1) (dry weight, dw) and 1377 ng g(-1) (dw), respectively. The ranges for PHCs and total PAHs in the sediments from Xiamen Harbour were 133-943 microg g(-1) (dw) and 98-309 ng g(-1) (dw), respectively. Shipping activities, industrial wastewater discharges, fuel oil spillage from ships and vehicles were the main sources of PHCs and PAHs in the Harbour. In addition, the widespread use of coal for industrial processes and domestic consumption accounted for the second largest source of PAHs in the sediments, while atmospheric transport and deposition of PAHs are also important.     

Agricultural reuse of reclaimed water and uptake of organic compounds: pilot study at Mutah University wastewater treatment plant, Jordan

The residues of polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated benzenes (CBs) and phenols were investigated for soil, wastewater, groundwater and plants. The uptake concentration of these compounds was comparatively determined using various plant types: Zea mays L., Helianthus annus L., Capsicum annum L., Abelmoschus esculentus L., Solanum melongena L. and Lycopersicon esculentum L. which were grown in a pilot site established at Mutah University wastewater treatment plant, Jordan. Soil, wastewater, groundwater and various plant parts (roots, leaves and fruits) samples were extracted in duplicate, cleaned up by open-column chromatography and analyzed by a multi-residue analytical methods using gas chromatography equipped with either mass selective detector (GC/MS), electron capture detector (GC/ECD), or flame ionization detector (FID). Environmentally relevant concentrations of targeted compounds were detected for wastewater much higher than for groundwater. The overall distribution profiles of PAHs and PCBs appeared similar for groundwater and wastewater indicating common potential pollution sources. The concentrations of PAHs, PCBs and phenols for different soils ranged from 169.34 to 673.20 microg kg(-1), 0.04 to 73.86 microg kg(-1) and 73.83 to 8724.42 microg kg(-1), respectively. However, much lower concentrations were detected for reference soil. CBs were detected in very low concentrations. Furthermore, it was found that different plants have different uptake and translocation behavior. As a consequence, there are some difficulties in evaluating the translocation of PAHs, CBs, PCBs and phenols from soil-roots-plant system. The uptake concentrations of various compounds from soil, in which plants grown, were dependent on plant variety and plant part, and they showed different uptake concentrations. Among the different plant parts, roots were found to be the most contaminated and fruits the least contaminated.     

Spatial uncoupling of biodegradation, soil respiration, and PAH concentration in a creosote contaminated soil

Hotspots and coldspots of concentration and biodegradation of polycyclic aromatic hydrocarbons (PAHs) marginally overlapped at the 0.5-100 m scale in a creosote contaminated soil in southern Sweden, suggesting that concentration and biodegradation had little spatial co-variation. Biodegradation was substantial and its spatial variability considerable and highly irregular, but it had no spatial autocorrelation. The soil concentration of PAHs explained only 20-30% of the variance of their biodegradation. Soil respiration was spatially autocorrelated. The spatial uncoupling between biodegradation and soil respiration seemed to be governed by the aging of PAHs in the soil, since biodegradation of added ¹³C phenanthrene covaried with both soil respiration and microbial biomass. The latter two were also correlated with high concentrations of phospholipid fatty acids (PLFAs) that are common in gram-negative bacteria. However, several of the hotspots of biodegradation coincided with hotspots for the distribution of a PLFA indicative of fungal biomass.     

Seasonal distribution and contamination levels of total PHCs, PAHs and heavy metals in coastal waters of the Alang-Sosiya ship scrapping yard, Gulf of Cambay, India

Alang-Sosiya situated on the Gulf of Cambay is one of the largest ship breaking yard in the world. The seasonal distribution and contamination levels of dissolved and/or dispersed total petroleum hydrocarbons (PHCs), total polycyclic aromatic hydrocarbons (PAHs) and heavy metals in seawater during high tide are investigated. The concentrations of petroleum hydrocarbons and heavy metals are higher in the winter than in the monsoon and summer. The concentrations of total PHCs and PAHs are about three times higher in the winter and two times in the monsoon or summer at Along-Sosiya and about twice in all seasons at two stations one on either side 5 km away from it as compared to the reference station at Mahuva, 60 km away towards the south. Further, the levels of PHCs are correlated with salinity and compared with those of other regions. The concentration of all metals is the highest in the winter season followed by the monsoon and summer. We carried out the quantitative analysis of the possible relationships among 13 variables such as Al, Fe, Pb, Mn, Cu, Zn, Cd, Cr, Co, pH, NO3-, NO2 and PO4(3-).     

Determination of PAHs in wastewater irrigated agricultural soil using accelerated solvent extraction

A procedure was developed for determination of 16 polycyclic aromatic hydrocarbons (PAHs) in heavily contaminated paddy soil from wastewater irrigated farmland near Tianjin. The sample was distilled with accelerated solvent extraction (ASE), purified by a silica gel column, and measured with GC/MS. The optimal conditions for the distillation were at 140 degrees C (1500 psi) with a 1:1 mixture of dichloromethane and acetone for 5 min. Application of cyclohexane for extract transfer improved the recovery when the ASE extraction was followed by a silica gel cleanup procedure. Recoveries from the method for 16 PAHs ranged from 57-140% with the coefficients of variation of the results ranging from 0.35% to 5.75%. The total 16 PAHs in a composite sample collected from a wastewater irrigated paddy field near Tianjin was 3.90 mg/kg.     

Polycyclic aromatic hydrocarbons in crude oil-contaminated soil: A two-step method for the isolation and characterization of PAHs

A two-step analytical method is developed for the isolation and characterization of polycyclic aromatic hydrocarbons (PAHs) in crude oil contaminated soil. In the first step, those crude oil components were isolated which are easily mobilized with water from the contaminated soil (determination of groundwater pollution potential). In the second step, the fraction containing the remaining crude oil compounds was extracted using toluene. After the cleanup of the fractions, both fractions were analyzed using high-performance liquid chromatography (HPLC). The HPLC of the toluene extracted fraction shows that along with the sixteen priority pollutants from the US-EPA list, many other polycyclic aromatic hydrocarbons (PAHs) are present as well. It is evident from the chromatograms that a significant amount of PAHs are present as is also the case in the fractions eluted by water. The described method allows the determination of total organic pollutants from crude oil, some of them being potential groundwater contaminants. The major part of the total pollutants could not be mobilized by water and therefore remains in the soil, which was extracted in the second step.     

Bioremediation of soil contaminated with polynuclear aromatic hydrocarbons (PAHs): a review

Polynuclear aromatic hydrocarbons (PAHs) constitute a group of priority pollutants which are present at high concentrations in the soils of many industrially contaminated sites. Criteria established for the removal or treatment or both of soils contaminated with PAHs vary widely within and between nations. The bioremediation of contaminated soils with in-situ, on-site, and bioreactor techniques is reviewed, together with the factors affecting PAH degradation. Current in-situ remediation techniques are considered ineffective for the removal of most PAHs from contaminated soil. On-site 'landforming' methods have been used successfully (and within a reasonable period of time) to degrade only those PAHs with three or fewer aromatic rings. Bioreactors have proved most effective for soil remediation, since conditions for enhanced degradation can be achieved most readily. However, bioreactors are still at the development stage, and further research is required to optimise their efficiency and economy for routine use. Degradation of the more recalcitrant high-molecular-weight PAHs is contaminated soil has not been particularly successful to date. Further research needs are identified to help develop bioremediation into a most cost-effective technology. The importance of full site assessments and treatability studies for successful application in the field is emphasised.     

Influence of Phenanthrene on Cadmium Toxicity to Soil Enzymes and Microbial Growth (5 pp)

Background Many contaminated sites contain a variety of toxicants. Risk assessment and the development of soil quality criteria therefore require information on the interaction among toxicants. Interactions between heavy metals are relatively well studied, but little is known about those between heavy metals and polycyclic aromatic hydrocarbons (PAHs). Methods 0.1 mg/kg dry soil phenanthrene alone or phenanthrene plus 10 mg/kg cadmium (Cd) were added to soil to determine the influence of phenanthrene on Cd toxicity to soil enzymes (invertase, urease, dehydrogenase and phosphatase) and microorganisms (fungi, bacteria and actinomycete) in paddy soil. Results and Discussion 0.1 mg/kg phenanthrene did not reduce the number of microorganisms. However, the addition of phenanthrene to soil with Cd enhanced the Cd toxicity to soil enzymes and microorganisms. This deleterious effect was seen to mainly affect the growth of fungi and the activity of invertase, urease and dehydrogenase. The order of combined inhibition of Cd and phenanthrene was fungi>bacteria>actinomycete. Conclusion The presence of phenanthrene might enhance the toxicity of Cd to soil microorganisms. Phenanthrene can easily be used by the soil actinomycetes as a source of carbon and energy and the finding may be supportive to the development of bioremediation techniques.     

PAHs in background soils from Western Europe: influence of atmospheric deposition and soil organic matter

The levels and distribution of polynuclear aromatic hydrocarbons (PAHs) were determined in soil samples from background locations in the UK and Norway, to investigate their spatial distribution and the controlling environmental factors. Concentrations ranged between 42 and 11200 microg kg(-1) (geometric mean 640 microg kg(-1)) and 8.6 and 1050 microg kg(-1) (150 microg kg(-1)) dry weight in the UK and Norwegian soil, respectively. Proximity to sources and locations susceptible to high atmospheric depositional inputs resulted in higher concentrations. Statistically significant relationships were observed between PAH and total organic carbon (TOC) in the Norwegian samples. High molecular weight PAHs correlated with black carbon (BC) in UK-woodland soil. These observations support the hypothesis that TOC plays an important role in the retention of PAHs in soil and that PAHs are often combined with BC during combustion emissions. PAHs with 4 and more rings comprised approximately 90% of total PAHs in the UK soil, but only 50% in the Norwegian soil. The mixture of PAHs implied that fractionation occurred during long-range atmospheric transport and deposition. The lighter PAHs with lower K(ow) values more readily reached the most remote sites. The heavier PAHs with higher K(ow) values remained in closer proximity to sources.     

Assessment of contaminant lability during phytoremediation of polycyclic aromatic hydrocarbon impacted soil

Polycyclic aromatic hydrocarbons (PAHs) are recalcitrant compounds, some of which are known carcinogens, often found in high residual soil concentrations at industrial sites. Recent research has confirmed that phytoremediation holds promise as a low-cost treatment method for PAH contaminated soil. In this study, the lability of soil bound PAHs in the rhizosphere was estimated using solid phase extraction resin. An extraction time of 14 days was determined to be appropriate for this study. Resin-extractable PAHs, which are assumed to be more bioavailable, decreased during plant treatments. Significant reductions in the labile concentrations of several PAH compounds occurred over 12 months of plant growth. The differences in concentration between the unplanted and the planted soil indicate that the presence of plant roots, in addition to the passage of time, contributes to reduction in the bioavailability of target PAHs.     

Priming effects on PAH degradation and ecotoxicity during a phytoremediation experiment

An experiment was conducted to distinguish priming effects from the effects of phytoremediation of a creosote-polluted soil. The concentration of 13 polycyclic aromatic hydrocarbons (PAHs), and their combined soil toxicity (using four bioassays), was determined on recently excavated, homogenized soil and on such soil subjected to a time-course phytoremediation experiment with lucerne. The results showed a high priming effect, with minor positive and synergistic effects of planting and fertilization on PAH degradation rates. At the end of the experiment, PAH degradation reached 86% of the initial 519 mg PAHs kg(-1). Two of the four toxicity tests (bioluminescence inhibition and ostracod growth inhibition) corroborated the chemical data for residual PAHs, and indicated a significant reduction in soil toxicity. We conclude that priming effects can easily surpass treatment effects, and that an unintentional pre-incubation that ignores these effects can jeopardize the full quantitative assessment of in situ bioremediation of contaminated soil.     

Polycyclic aromatic hydrocarbons in fuel-oil contaminated soils, Antarctica

Where fuel oil spills have occurred on Antarctic soils polycyclic aromatic hydrocarbons (PAH) may accumulate. Surface and subsurface soil samples were collected from fuel spill sites up to 30 years old, and from nearby control sites, and analysed for the 16 PAHs on the USEPA priority pollutants list, as well as for two methyl substituted naphthalenes, 1-methylnaphthalene and 2-methylnaphthalene. PAH levels ranged from 41-8105 ng g-1 of dried soil in the samples from contaminated sites and were below detection limits in control site samples. PAH were detected in surface soils and had migrated to lower depths in the contaminated soil. The predominant PAH detected were naphthalene and its methyl derivatives.     

Correlations between PAH bioavailability,degrading bacteria,and soil characteristics during PAH biodegradation in five diffusely contaminated dissimilar soils

The natural biodegradation of seven polycyclic aromatic hydrocarbons (PAHs) by native microorganisms was studied in five soils from Normandy (France) from diffusely polluted areas, which can also pose a problem in terms of surfaces and amounts of contaminated soils. Bioavailability tests using cyclodextrin-based extractions were performed. The natural degradation of low molecular weight (LMW) PAHs was not strongly correlated to their bioavailability due to their sorption to geosorbents. Conversely, the very low degradation of high molecular weight (HMW) PAHs was partly correlated to their poor availability, due to their sorption on complexes of organic matter and kaolinites or smectites. A principal component analysis allowed us to distinguish between the respective degradation behaviors of LMW and HMW PAHs. LMW PAHs were degraded in less than 2–3 months and were strongly influenced by the relative percentage of phenanthrene-degrading bacteria over total bacteria in soils. HMW PAHs were not significantly degraded, not only because they were less bioavailable but also because of a lack of degrading microorganisms. Benzo[a]pyrene stood apart since it was partly degraded in acidic soils, probably because of a catabolic cooperation between bacteria and fungi.     

Uptake of vapor and particulate polycyclic aromatic hydrocarbons by cabbage

Polycyclic aromatic hydrocarbons (PAHs) in cabbage (aerial part), air (gas and particles) and soil samples collected from two sites in Tianjin, China were measured. Although the levels of PAHs in all samples from the heavily contaminated site B were higher than those from the less contaminated site A, the PAH profiles were similar, suggesting the similarity in source type. PAH concentrations in cabbages were positively correlated to either gas or particle-bound PAHs in air. A multivariate linear regression with cabbage PAH as a function of both gas and particle-bound PAHs in air was established to quantitatively characterize the relationship between them. Inclusion of soil PAH concentrations would not improve the model, indicating that the contribution of soil PAHs to cabbage (aerial part) accumulation was insignificant.     

Pressure-assisted ozonation of PCB and PAH contaminated sediments

Sediment contamination by recalcitrant organics such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) is prevalent and of a great concern. Remediation efforts are hampered by the hydrophobic nature of the contaminants that limits their availability as well as by the sediment matrix that limits their exposure to treatment agents. Using contaminated sediment samples from the Passaic River, St. Louis River, Waukegan Harbor, and Wells National Estuarine Research Reserve, this research demonstrated a new ozonation technique that incorporates rapid, successive cycles of pressurization (690 kPa) and depressurization, enabling more effective treatment than conventional ozonation would. Conventional ozonation reached maximum 60% and 40% removal of PAHs from the Passaic River (40 mg kg(-1) initially) and St. Louis River sediment (520 mg kg(-1) initially), respectively, in 1h; however, removals ceased despite prolonged treatment for 2h. The pressure-assisted technique removed 96% of PAHs from both river sediments within 1h; it completely removed both PAHs (16 mg kg(-1) initially) and PCBs (5.1 mg kg(-1) initially) from the Waukegan Harbor sediment in 0.5 h. The heightened treatment is explained by soil aggregate fracturing upon pressure cycles that exposes the contaminants as well as by the confluence of hydrophobic contaminants and O(3) at the gas-liquid interface in the presence of microbubbles. The technique is expected to accelerate O(3) treatment of a wide range of organic contaminants, and it may provide treatment to dredged and stored contaminated sediment.     

Phytoremediation of an aged petroleum contaminated soil using endophyte infected and non-infected grasses

Phytoremediation is a promising technique for cleaning petroleum contaminated soils. In this study, the effects of two grass species (Festuca arundinacea Schreb. and Festuca pratensis Huds.), infected (E(+)) and non-infected (E(-)) by endophytic fungi (Neotyphodium coenophialum and Neotyphodium uncinatum, respectively) on the degradation of petroleum hydrocarbons in an aged petroleum contaminated soil was investigated. Plants were grown in the soil for 7 months and unplanted soil considered as control. At the end of the experiment, total and oil-degrading bacteria, dehydrogenase activity, water-soluble phenols, total petroleum hydrocarbons (TPH) and polycyclic aromatic hydrocarbons (PAHs) contents were measured in the soil. The results demonstrated that E(+) plants contained more root and shoot biomass than E(-) plants and created higher levels of water-soluble phenols and dehydrogenase activity in the soil, while there was no significant difference in bacterial counts of planted soils. Planting stimulated total and oil-degrading bacterial numbers, dehydrogenase activity and the soil content of water-soluble phenols. Regardless of endophyte infection, PAH and TPH removal in the rhizosphere of plants were 80-84 and 64-72% respectively, whereas the removals in controls were 56 and 31%, respectively. It was revealed that TPHs in retention time range of n-alkanes with C(10)-C(25) chain lengths and TPH were more degraded in the rhizosphere of E(+) plants compared to E(-) ones. Thus, grasses infected with endophytic fungi could be more efficient for removal of TPH from oil-contaminated soils.     

Monitoring of the total content of polycyclic aromatic hydrocarbons (PAHs) in arable soils in Poland

The paper provides comprehensive information on the level of contamination of arable soils in Poland with polycyclic aromatic hydrocarbons (PAHs). Extensive monitoring studies were carried out to determine the content of the 16 priority PAHs in 216 soil samples collected in 2005 throughout arable lands (0-20 cm layer) in Poland. Locations of sampling points reflected the differences in regional industrialisation and urbanisation as well as in the characteristics of soils. The content of Sigma16PAHs ranged from 80 to 7264 microg kg(-1) with a median of 395 microg kg(-1) and with a dominance of 4-6 rings hydrocarbons (74% of total PAHs). Soil properties affected the PAHs content to a limited extend. The organic matter content was the only parameter correlated significantly (although weakly) with the concentrations of Sigma16PAHs; the strength of this relationship was more pronounced in soils with elevated OM content. The various molecular markers pointed to a prevailing pyrogenic origin of the PAHs in Polish arable soils, with minor contribution from liquid fuels combustion and traffic emissions. Two different Polish systems for classification of agricultural soils (providing for the content of Sigma9PAHs and Sigma13PAHs) indicate that the percentage of contaminated arable soils in Poland does not exceed 10%. Multivariate methods enabled an evaluation of spatial trends in Sigma16PAHs concentrations, an identification of regions with very low PAHs content (East part of the country), and a recognition of small industrial/urbanised areas of higher risk.