Characterization and Sources of PAHs and Potentially Toxic Metals in Urban Environments of Sevilla (Southern Spain)

The purpose of this study was to determine the degree of PAH contamination and the association of PAHs with metals in urban soil samples from Sevilla (Spain). Fifteen polycyclic aromatic hydrocarbons-PAHs (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, indeno[1,2,3-c,d]pyrene) and seven metals (Cd, Cr, Cu, Mn, Ni, Pb, Zn) have been evaluated in representative urban soil samples. Forty-one top soils (0–10 cm) under different land use (garden, roadside, riverbank and agricultural allotment) were selected. PAHs from soil samples were extracted by sonication using dichloromethane. The simultaneous quantification of 15 different PAH compounds were carried out by HPLC using multiple wavelength shift in the fluorescence detector. For qualitative analysis a photo diode-array detector was used. Metal (pseudo-total) analysis was carried out by digestion of the soils with aqua regia in microwave oven. The mean concentration of each PAH in urban soils of Sevilla showed a wide range, they are not considered highly contaminated. The results of the sum of 15 PAHs in Sevilla soils are in the range 89.5–4004.2 μg kg^?1, but there seems not to be a correlation between the concentration of PAHs and the land use. Of the 15 PAHs examined, phenanthrene, fluoranthene and pyrene were present at the highest concentrations, being the sum of these PAHs about 40% of the total content. Although metal content were not especially high in most soils, there are significant hints of moderate pollution in some particular spots. Such spots are mainly related with some gardens within the historic quarters of the city. The associations among metals and PAHs content in the soil samples was checked by principal components analysis (PCA). The largest values both for ‘urban’ metals (Pb, Cu and Zn) and for PAHs were mainly found in sites close to the historic quarters of the city in which a heavy traffic of motor vehicles is suffered from years.     

Influence of mixtures of acenaphthylene and benzo[a]anthracene on their degradation by Pleurotus ostreatus in sandy soil

Purpose

Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds commonly found as soil contaminants. Fungal degradation is considered as an environmentally friendly and cost-effective approach to remove PAHs from soil. Acenaphthylene (Ace) and Benzo[a]anthracene (BaA) are two PAHs that can coexist in soils; however, the influence of the presence of each other on their biodegradation has not been studied. The biodegradation of Ace and BaA, alone and in mixtures, by the white rot fungus Pleurotus ostreatus was studied in a sandy soil.

Materials and methods

Experimental microcosms containing soil spiked with different concentrations of Ace and BaA were inoculated with P. ostreatus. Initial (t ₀) and final (after 15 days of incubation) soil concentrations of Ace and BaA were determined after extraction of the PAHs.

Results and discussion

P. ostreatus was able to degrade 57.7% of the Ace in soil spiked at 30 mg kg^?1 dry soil and 65.8% of Ace in soil spiked at 60 mg kg^?1 dry soil. The degradation efficiency of BaA by P. ostreatus was 86.7 and 77.4% in soil spiked with Ace at 30 and 60 mg kg^?1 dry soil, respectively. After 15 days of incubation, there were no significant differences in Ace concentration between soil spiked with Ace and soil spiked with Ace + BaA, irrespective of the initial soil concentration of both PAHs. There were also no differences in BaA concentration between soil spiked with BaA and soil spiked with BaA + Ace.

Conclusions

The results indicate that the fungal degradation of Ace and BaA was not influenced by the presence of each other’s PAH in sandy soil. Bioremediation of soils contaminated with Ace and BaA using P. ostreatus is a promising approach to eliminate these PAHs from the environment.     

湿热灭菌和氯化汞灭菌对双液相体系中PAHs降解的影响

A two-liquid-phase(TLP) soil slurry system was employed to quantify the efficiencies of autoclaving and mercuric chloride sterilization in the dissipation of polycyclic aromatic hydrocarbons(PAHs).The fates of 11 PAHs(naphthalene,fluorene,phenanthrene,anthracene,fluoranthene,pyrene,benzo(a)anthracene,benzo(a)pyrene,benzo(b)fluoranthene,benzo(k)fluoranthene,dibenzo(a,h)anthracene) were recorded over 113 days of incubation.No microorganisms were detected in the HgCl 2-sterilized soil slurries during the whole incubation period,indicating very effective sterilization.However,about 2%-36% losses of PAHs were observed in the HgCl 2 sterilized slurry.In contrast to the HgCl 2-sterilized soil slurry,some microorganisms survived in the autoclaved soil slurries.Moreover,significant biodegradation of 6 PAHs(naphthalene,fluorene,phenanthrene,anthracene,fluoranthene and pyrene) was observed in the autoclaved soil slurries.This indicated that biodegradation results of PAHs in the soil slurries,calculated on basis of the autoclaved control,would be underestimated.It could be concluded that the sterilization efficiency and effectiveness of HgCl 2 on soil slurry was much higher than those of autoclaving at 121℃ for 45 min.     

Estimation of PAH bioavailability to Lepidium sativum using sequential supercritical fluid extraction – a case study with industrial contaminated soils

For the determination of PAH availability to plants a plant accumulation test with Lepidium and sequential supercritical fluid extraction (SSFE) with carbon dioxide as extraction solvent was used, during which the extraction conditions were changed from mild to harsh in order to represent a broad range of potential pollutant-soil interactions. Both approaches were applied in laboratory experiments on industrial contaminated soils which, in addition, were also freshly spiked with PAHs in order to increase the bioavailability. Only Naphthalene, Phenanthrene and, in some cases, Pyrene accumulated from the industrial contaminated soils. Accumulation experiments with spiked industrial soils showed that other PAHs, for example Anthracene, Fluorene and even high weight PAHs like Benzo(a)pyrene, also could be taken up by plants. SSFE extraction data were compared to accumulated amounts of PAHs in the plants. Strong correlations were found for Phenanthrene between plant accumulation and extractability under very mild extraction conditions. For Naphthalene, accumulation did not correlate with its extractability in the industrial soils. The possibility exists that bioavailability in soil was eclipsed by an accumulation in the gas phase due to the high volatility of Naphthalene. Supercritical fluid extraction appears to be a promising tool to estimate Phenanthrene availability to plants, but further studies for the evaluation of other PAHs are recommended. This could be helpful for the determination of the feasibility of phytoremediation applications on industrially contaminated soils.     

Effect of soil pollution with polycyclic aromatic hydrocarbons on the properties of humic acids

Purpose

Interestingly, soil is the component of the natural environment in which most hydrophobic organic pollution including polycyclic aromatic hydrocarbons (PAHs) gets accumulated. The aim of the present paper was to determine the effect of soil pollution with PAHs on the elemental composition, spectral properties, and hydrophobic and hydrophilic properties of humic acids. The research was performed on different types of soil samples that were artificially polluted with selected PAHs (anthracene, pyrene, fluorene and chrysene).

Materials and methods

The soil samples were polluted with selected PAHs in an amount corresponding to 10 mg PAHs kg^?1. The PAHs-polluted soil samples were incubated for 180 and 360 days at a temperature of 20–25 °C and fixed moisture (50 % of field water capacity). Humic acids (HAs) were extracted from the soil samples prior to the incubation (additionally, soils not polluted with PAHs) and after 180 and 360 days of incubation. For isolated HAs, the following analyses were performed: elemental composition, UV–Vis and IR spectra, susceptibility to oxidation, and hydrophilic (HIL) and hydrophobic (HOB) properties were determined using high-performance liquid chromatography.

Results and discussion

The research demonstrated that introducing anthracene, fluorene, pyrene and chrysene to soil samples resulted in a change in some of the quality parameters of humic acids. However, the intensity and the direction of those changes were determined by soil properties. The changes of the parameters, once PAHs were introduced, that did not depend on the soil properties were ΔA _665u and ΔA _465u (susceptibility to oxidation at wavelengths of 465 and 665 nm) as well as HIL/ΣHOB. The same tendency in changes in the structure of humic acids, once PAHs were introduced, was also observed based on the Fourier transform infrared spectra pattern.

Conclusions

A single pollution of soils with PAHs that leads to changes in the quality parameters of humic acids shows that, as for the soils permanently exposed to pollution with those compounds, significant changes can occur in the properties of humic acids. As a result, it can lead to a change in the functions played by humic acids in the environment.     

Prediction of Polycyclic Aromatic Hydrocarbon Bioaccessibility to Earthworms in Spiked Soils by Composite Extraction with Hydroxypropyl-β-Cyclodextrin and Organic Acids

Traditional exhaustive extraction methods often overestimate the risk of polycyclic aromatic hydrocarbon(PAH) bioaccessibility to biota. Therefore, reliable assessment methods need to be established. In this study, a composite extraction with hydroxypropyl-β-cyclodextrin(HPCD) and three low-molecular-weight organic acids, oxalic acid(OA), malic acid(MA), and citric acid(CA), was used to predict the PAH bioaccessibility to earthworms, subjecting to two soils(red soil and yellow soil) spiked with selected PAHs,phenanthrene, pyrene, chrysene, benzo(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene. For both soils,concentrations of PAHs by composite extraction using HPCD-OA(R~2= 0.89–0.92, slope = 1.89–2.03; n = 35), HPCD-MA(R~2=0.92–0.96, slope = 1.43–1.67; n = 35), and HPCD-CA(R~2= 0.92–0.96, slope = 1.26–1.56; n = 35) were significantly correlated with PAH accumulation in the Eisenia fetida earthworms. Moreover, the HPCD-CA-and HPCD-MA-extracted PAH concentrations were closer to the earthworm-accumulated PAH concentration than the extraction using just HPCD. The results indicated that the composite extraction could improve the prediction of PAH bioaccessibility, and therefore can serve as a reliable chemical method to predict PAH bioaccessibility to earthworms in contaminated soils.     

天津表土中多环芳烃含量的空间分布特征与来源

采用聚类分析、方差分析和多重比较等统计方法,结合空间分异分析研究了天津表土中多环芳烃(PAHs)含量的多元和空间分布特征。结果表明,可根据样点PAHs含量和空间分布特征将天津地区划分为三个含量有显著差异且连续分布的区域,即南北低值区、市中心近郊次高值区和塘沽汉沽高值区。三区除PAHs含量有显著差别外,16种PAHs化合物的谱分布也有显著不同。根据不同化合物的含量关系及天津地区燃料消耗资料可以判定,南北低值区土壤中PAHs基本来自燃煤排放,而两个高值区污染来源复杂,除燃煤仍是主要来源外,其他重要来源还包括燃油和其他工业活动。     

Polycyclic Aromatic Hydrocarbons in Soils from European High Mountain Areas

Polycyclic aromatic hydrocarbons (PAHs) were analyzed in 70 soils distributed in mountain areas such as Montseny (300?C1,700 m), Pyrenees (1,500?C2,900 m), Alps (1,100?C2,500 m), and Tatras (1,400?C1,960 m). Average total PAH concentrations, excluding retene and perylene, were about 400 ng/g in the Pyrenees and 1,300?C1,600 ng/g in the other mountain ranges. No correlations between PAH concentrations and total organic carbon were observed. Retene was the major PAH in the Pyrenean soils of lower altitude. No altitudinal dependence was found between soil PAH concentrations and elevation for the whole dataset. However, in the Tatra soils a statistically significant correlation with altitude was observed involving higher concentrations at higher altitude. This correlation was due to the statistically significant altitudinal dependence of the more volatile PAHs. Another observed altitudinal trend concerned the benz[a]anthracene/(benz[a]anthracene + chrysene + triphenylene) and the benzo[a]pyrene/(benzo[a]pyrene + benzo[e]pyrene) ratios that exhibited a decrease in the more chemically labile compounds, benz[a]anthracene and benzo[a]pyrene, respectively, in the soils located at higher altitude. This observation is consistent with the expected higher photooxidation at higher mountain altitude.     

Relationship Between Soil Concentrations of PAHs and Their Regional Emission Indices

Actual information on the level of accumulation of PAHs in soils, their inputs/outputs and fate is still unsatisfactory. The regional scale of data collection is important from practical point of view, since decisions regarding environment protection often require proper assessment of soil information aggregated on this level. The objective of the study was to define the regional levels of PAHs in soils and to examine the relationship with the parameters related to their inputs (emission factors) and to natural conditions (soil properties, geographical localisation). The territory of Poland, comprising 16 regions, was chosen as a model area representing the Central/East European countries. The concentrations of 16 PAH compounds were determined in 266 soil samples collected from 0 to 30-cm upper soil layer from agricultural lands. The data were supplemented with basic soil properties. The regional concentrations of Σ16PAHs were within the limits of 125–756 μg kg^?1 (geometric means) and did not exceed the limit values specified in Polish regulations. They complied also with European soil screening values for intermediate or negligible risk. The key variable affecting the accumulation of PAHs in soils was the regional emission of those contaminants, which described soil concentrations of PAHs in at least 50%; the results suggest time-dependent (delayed) reaction of soil environment to the emission changes. The effect was sensitive to PAH compositions in soils and was most pronounced in the case of higher molecular weight compounds (≥4 rings) transported predominantly with atmospheric particles. The regression models, comprising actual regional emission data, did not indicated on the increasing risk of PAHs accumulation in soils. The evaluations based on the regional content of benzo(a)pyrene in soils implied significant discrepancies between Polish and other internationally accepted criteria in soil contamination. The natural factors (soil characteristics and climate) affected the regional PAH concentrations in very small extent.     

土壤中多环芳烃的分布特征及其来源分析

利用气相色谱法分析了南充市10个不同功能区表层土壤中美国环保署规定的16种优控多环芳烃（PAHs）的含量和组分特征,运用同分异构体比率揭示了其污染来源。研究表明,该区土壤中PAHs的含量在9.1～2269.1μg·kg-1之间,而且工业区的残留量大于农业区和居民区的残留量。按PAHs的环数来分,在工业污染区PAHs的含量总的趋势是四环〉二环〉三环〉五环〉六环;农业和居民区二环〉三环〉五环〉四环〉六环。该污染状况与国内外相关研究比较,处于中等污染水平。煤、木材和化石的燃烧是该地区土壤中PAHs污染的主要来源,苯并（a）蒽和菲是主要的超标化合物。     

南京有机污染风险区农田土壤多环芳烃污染状况研究

采集南京地区不同有机污染风险区农田表层土壤,用超快速液相色谱仪检测样品中15种EPA优控的多环芳烃(PAHs)含量。结果表明,被检农田土壤多环芳烃总量分布于306.0~1251.3μg kg~(-1)之间,均值682.0μg kg~(-1),四环以上高环多环芳烃占较大比例(80%)。根据欧洲土壤质量标准,所检土壤样本已达污染水平。不同风险污染区农田土壤PAHs的含量由高至低为:钢铁工业区、有机垃圾处理区、化工工业区及炼油工业区。钢铁工业区附近主要的污染物为荧蒽、芘、屈和苯并[a]蒽,分别占到污染物总量的16%、13%、10%和10%。采用荧蒽/(荧蒽+芘)与茚并[1,2,3-cd]芘/(茚并[1,2,3-cd]芘+苯并[g,h,i]苝)比值对各地污染物来源进行分析,结果发现调查区域的PAHs污染物以燃烧源为主,生物质燃料为主要污染物,部分地区同时有石油燃烧污染。     

Dissipation of polycyclic aromatic hydrocarbons (PAHs) in soil microcosms amended with mushroom cultivation substrate

The potential of mushroom cultivation substrate (MCS) in bioremediation was examined in polycyclic aromatic hydrocarbon (PAH)-contaminated soil. After a 60-day incubation, 32.9% dissipation of the 15 studied PAHs was observed in MCS-amended microcosms, with anthracene, benzo(a)pyrene and benzo(a)anthracene being the most degradable PAHs. MCS significantly increased the abundance and changed the community compositions of bacteria, fungi and aromatic hydrocarbon degraders. Two species belonging to the Sordariomycetes of the Ascomycota were enriched in all MCS-treated soil samples, and coupled with the unique changes in the PAH profile, this implies the involvement of laccase-like enzymes. Limited improvement was observed after adding Pleurotus ostreatus, possibly because of its poor colonization of the soil. In addition, alfalfa appeared to antagonize the bioremediation effects of MCS. The results of this study suggest that MCS can be a cost-effective and green biostimulation agent, thereby providing support for the development of MCS-based biostimulation of PAH-contaminated soil.     

Input and behavior of polycyclic aromatic hydrocarbons in arable,fallow, and forest soils of the taiga zone (Tver oblast)

Contents of 11 most prevalent polycyclic aromatic hydrocarbons (PAHs) in snow and soils of arable, fallow, and forest areas significantly remote from impact technogenic sources of polyarenes have been examined in the Torzhok district of Tver oblast. From the analysis of snow samples, the volumes and composition of PAHs coming from the atmosphere onto the areas of different land use have been determined. Light hydrocarbons prevail in PAHs. They make up 65–70% of total PAHs; their share in soils reaches almost 95%. An increase in the content of PAHs is revealed in fallow soils compared to arable and afforested areas. A direct relationship is revealed between the lateral distribution of total PAHs and the content of organic carbon. The distribution of total PAHs is surface-accumulative in forest soils, mainly uniform in arable soils, and deepaccumulative in fallow soils. PAH groups characterized by similar radial distributions and ratios between their reserves in snow and soils are distinguished: (1) fluorene and phenanthrene, (2) biphenyl and naphthalene, (3) benzo(a)anthracene, chrysene, perylene, and benzo[a]pyrene, and (4) anthracene and benzo[ghi]pyrene.     

混合菌降解土壤中多环芳烃的试验研究

PAHs生物降解程度受多种因素影响。通过筛选驯化PAHs降解菌,研究混合菌对土壤中菲、芘、苯并（a）蒽、苯并（b）荧蒽、苯并（k）荧蒽、茚并（1,2,3-cd）芘的生物降解性能,并考察污染时间对土壤中PAHs降解效果的影响。结果表明,筛选的混合菌具有很强的PAHs降解能力,缩短了PAHs生物降解的半衰期,且PAHs起始降解速率较快,之后趋于平缓。27d内土壤中的菲、芘、苯并（a）蒽、苯并（b）荧蒽、苯并（k）荧蒽、茚并（1,2,3-cd）芘的平均降解率分别为98.14%、89.97%、88.47%、63.55%、65.24%、60.49%,其中菲在5d之内的降解率高于93%。污染210d的土壤中各PAHs的起始降解速率高于污染50d的土壤,因此污染时间越长,PAHs生物降解的停滞期越短。     

Comparison of Fenton's Reagent and Ozone Oxidation of Polycyclic Aromatic Hydrocarbons in Aged Contaminated Soils (7 pp)

Background, Aim and Scope   Polycyclic aromatic hydrocarbons (PAHs) are formed as a result of incomplete combustion and are among the most frequently occurring contaminants in soils and sediments. PAHs are of great environmental concern due to their ubiquitous nature and toxicological properties. Consequently, extensive research has been conducted into the development of methods to remediate soils contaminated with PAHs. Fenton's reagent or ozone is the most commonly studied chemical oxidation methods. However, the majority of remediation studies use soils that have been artificially contaminated with either one or a limited number of PAH compounds in the laboratory. Hence, it is essential to extend such studies to soils contaminated with multiple PAHs under field conditions. Objectives   The objective of this study is to investigate the capacity of Fenton's reagent and ozone to degrade PAHs in soils. The soils have been collected from a number of different industrial sites and, therefore, will have been exposed to different PAH compounds in varying concentrations over a range of time periods. The capacity of Fenton's reagent and ozone to degrade PAHs in industrially contaminated soils is compared to results obtained in studies using soils artificially contaminated with PAHs in the laboratory. Materials and Methods: Nine soil samples, contaminated with PAHs, were collected from five different industrial sites in Sweden. For the Fenton's reagent procedure, the pH of the soil slurry samples was adjusted to pH 3 and they were kept at a constant temperature of 70oC whilst H2O2 was added. For the ozone procedure, soil samples were mixed with 50% water and 50% ethanol and kept at a constant temperature of 45 oC. Ozone was then continually introduced to each soil sample over a period of four hours. Following the Fenton's reagent and ozone oxidation procedures, the samples were filtered to isolate the solid phase, which was then extracted using pressurized liquid extraction (PLE). The sample extracts were cleaned up using open columns and then analysed by gas chromatography-mass spectrometry (GC-MS). Results: The relative abundance of the detected PAHs varied between soils, associated with different industries. For example, low molecular weight (LMW) PAHs were more abundant in soil samples collected from wood impregnation sites and high overall PAH degradation efficiencies were observed in soils originating from these sites. In the contaminated soils studied, PAHs were more effectively degraded using Fenton's reagent (PAH degradation efficiency of 40-86%) as opposed to ozone (PAH degradation efficiency of 10-70%). LMW PAHs were more efficiently degraded, using ozone as the oxidizing agent, whereas the use of Fenton's reagent resulted in a more even degradation pattern for PAHs with two through six fused aromatic rings. Discussion: The degradation efficiency for both methods was largely dependent on the initial PAH concentration in the soil sample, with higher degradation observed in highly polluted soils. LMW PAHs are more susceptible to degradation than high molecular weight (HMW) PAHs. As a result of this the relative abundance of large (often carcinogenic) PAHs increased after chemical oxidation treatment, particularly after ozone treatment. Repeated Fenton's reagent treatment did not result in any further degradation of soil PAHs, indicating that residual soil PAHs are strongly sorbed. The effectiveness of the two oxidation treatment approaches differed between industrial sites, thus highlighting the importance of further research into the influence of soil properties on the sorption capacity of PAHs. Conclusions: This study demonstrates that the degree to which chemical oxidation techniques can degrade soil bound PAHs chemical degradation is highly dependent on both the concentration of PAHs in the soils and the compounds present, i.e. the various PAH profiles. Therefore, similarities in the PAH degradation efficiencies in the nine soil samples studied were observed with the two chemical oxidation methods used. However, the degradation performance of Fenton's reagent and ozone differed between the two methods. Overall, Fenton's reagent achieved the highest total PAH degradation due to stronger oxidation conditions. LMW PAHs showed higher susceptibility to oxidation, whereas high molecular weight (HMW) PAHs appear to be strongly sorbed to the soils and therefore less chemically available for oxidation. This study highlights the importance of including soils collected from a range of contaminated sites in remediation studies. Such soil samples will contain PAH contaminants of varying concentrations, chemical and physical properties, and have been aged under field conditions. In addition to the chemical and physical properties of the soils, these factors will all influence the chemical availability of PAHs to oxidation. Recommendations and Perspectives: We recommend including aged contaminated soils in chemical degradation studies. In future chemical remediation work, we intend to investigate the potential influence of the chemical and physical properties of PAHs and soil parameters potential influence on the chemical oxidation efficiency in aged contaminated soils. Due to the vast number of contaminated sites there is a great need of efficient remediation methods throughout the world. This study shows the difficulties which may be experienced when applying remediation methods to a variation of contaminated sites.     

某氮肥厂场地土壤PAHs污染特征研究

采用现场采样及室内测试方法对广州某氮肥厂原料车间和油库区土壤中16种优控多环芳烃（PAHs）的含量进行调查研究,分析了EPAHs含量及其组成特征和垂直分布特征,并在此基础上进行了源解析。结果表明,分析样品中∑PAHs范围在10-7795μg·kg,原料车间土壤中的∑PAHs小于油库区土壤中的,菲、芘、荧蒽、并（b）荧蒽、苯并（a）芘为主要污染物;油库土壤0-40cm的样品中16种PAHs均有检出,∑PAHs和单体分布基本一致;原料车间土壤∑PAHs和单体浓度随着地面深度的增加而减少。通过对单组分比值（菲／蒽,荧蒽／芘）的分析可以看出油库区土壤中PAHs来源于石油和燃烧源,而原料车间污染源主要为燃烧源。     

Potential role of polycyclic aromatic hydrocarbons (PAHs) oxidation by fungal laccase in the remediation of an aged contaminated soil

The transformation of PAHs by fungal laccases has been reported but there are no published studies on the direct application of free laccase in the remediation of PAHs-contaminated soil. Here we report a study in which the transformation of PAHs by a fungal laccase was studied both in reaction mixtures and in soil. Anthracene and benzo(a)pyrene were the most degradable of the 15 US Environmental Protection Agency (EPA) priority PAHs tested. Use of a redox mediator greatly enhanced the oxidation of several PAHs in reaction mixtures and the main intermediates were identified as anthraquinone for anthracene and benzo(a)pyrenyl acetate for benzo(a)pyrene as determined by GC–MS analysis. No significant correlation was found between oxidation and ionization potentials of individual PAHs. Soil microcosms were set up to test the potential of laccase to remediate an aged PAHs-contaminated soil. The laccase transformed the PAHs immediately after it was added to the soil and significant dissimilation of benzo(a)pyrene and toxic-equivalent concentration based on benzo(a)pyrene was observed after incubation for 14 days, indicating the potential of laccase to detoxify the soil. Moreover, extractable laccase activity was completely lost and the biomass of the indigenous microorganisms remained constant in the microcosms at the end of the incubation period, suggesting that the enzyme may have potential as an agent for the efficient and safe cleanup of soil contaminated with PAHs.     

Bioaugmentation and biostimulation effects on PAH dissipation and soil ecotoxicity under controlled conditions

The degradation of spiked anthracene (ANT), pyrene (PYR) and benzo[a]pyrene (B[a]P) in soil (3000 mg ∑ 3 PAHs kg⁻¹ dry soil) was studied in aerobically incubated microcosms for 120 d. The applied treatments aimed at enhancing PAH removal from the heavily contaminated soils are: (i) bioaugmentation by adding aged PAH-contaminated soil (ACS) containing activated indigenous degraders; and (ii) combined bioaugmentation/biostimulation by incorporating sewage sludge compost (SSC) and decaying rice straw (DRS). The adopted treatments produced higher PAH dissipation rates than those observed in unamended PAH-spiked soils, especially for ANT and PYR in the presence of DRS or ACS (>96%). However, B[a]P was the most recalcitrant hydrocarbon to biodegradation. Extracellular enzyme investigation revealed the existence of ligninolytic activities in all soil treatments, including control but no relationship could be found with PAH dissipation. The ecotoxicological assessment indicated that regardless of applied treatment, PAH-spiked soils were chronically lethal to ostracod Heterocypris incongruens and confirmed the sensitivity of the microcrustacean to the concomitant presence of these three hydrocarbons. Lettuce root elongation inhibition was correlated with PAH level but the presence of SSC conferred a strong phytotoxic capacity to PAH-spiked soils. DRS amendment may constitute a cost-effective alternative for hydrocarbon bioremediation as it has impacted positively on soil microbial activity and enhanced PAH removal with no apparent changes in soil physico-chemical properties.