Polycyclic aromatic hydrocarbon storage in a typical Cerrado of the Brazilian savanna

There may be important biological sources of polycyclic aromatic hydrocarbons (PAHs) to the global environment, particularly of naphthalene, phenanthrene, and perylene, that originate in the tropics. We (i) studied the distribution of PAHs among different compartments of a typical Cerrado to locate their sources and (ii) quantified the PAH storage of this ecosystem. The sum of 20 PAH (sigma20PAHs) concentrations ranged from 25 to 666 microg kg(-1) in plant tissue, 7.4 to 32 microg kg(-1) in litterfall, 206 to 287 microg kg(-1) in organic soil, and 10 to 79 microg kg(-1) in mineral soil. Among the living biomass compartments, the bark had the highest mean PAH concentrations and coarse roots the lowest, indicating that PAHs in the plants originated mainly from aboveground sources. Naphthalene and phenanthrene were the most abundant individual PAHs, together contributing 33 to 96% to the sigma20PAHs concentrations. The total storage of the X20PAHs in Cerrado was 7.5 mg m(-2) to a 0.15-m soil depth and 49 mg m(-2) to a 2-m soil depth. If extrapolated to the entire Brazilian Cerrado region, roughly estimated storages of naphthalene and phenanthrene correspond to 7300 and 400 yr of the published annual emissions in the United Kingdom, respectively. The storage of benzo[a]pyrene, a typical marker for fossil fuel combustion, in the Cerrado only corresponds to 0.19 yr of UK emissions. These results indicate that the Brazilian savanna comprises a huge reservoir of naphthalene and phenanthrene originating most likely from the aboveground parts of the vegetation or associated organisms. Thus, the Cerrado might be a globally important source of these PAHs.     

Phytoremediation of polycyclic aromatic hydrocarbons in manufactured gas plant-impacted soil

Contamination of soil by hazardous substances poses a significant threat to human, environmental, and ecological health. Cleanup of the contaminants using destructive, invasive technologies has proven to be expensive and more importantly, often damaging to the natural resource properties of the soil, sediment, or aquifer. Phytoremediation is defined as the cleanup of contaminated sites using plants. There has been evidence of enhanced polycyclic aromatic hydrocarbons (PAHs) degradation in rhizosphere soils for a limited number of plants. However, research focusing on the degradation of PAHs in the rhizosphere of trees is lacking. The objective of this study was to assess the potential use of trees to enhance degradation of PAHs located in manufactured gas plant-impacted soils. In greenhouse studies with intact soil cores, acenaphthene, anthracene, fluoranthene, naphthalene, and phenanthrene decreased significantly (p < 0.05) in green ash (Fraxinus pennsylvanica Marshall) and hybrid poplar (Populus deltoides x P. nigra DN 34) phytoremediation treatments when compared to the unplanted soil control. Increases in PAH microbial degraders in rhizosphere soil were observed when compared to unvegetated soil controls. In addition, the rate of degradation or biotransformation of PAHs was greatest for soils with black willow (Salix nigra Marshall), followed by poplar, ash, and the unvegetated controls. These results support the hypothesis that a variety of plants can enhance the degradation of target PAHs in soil.     

Ecotoxic effect of phenanthrene on nitrifying bacteria in soils of different properties

Information on ecotoxicity of organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), in terrestrial environment is needed for establishing soil quality criteria and for risk assessment purposes. An ecotoxic effect of a model PAH compound (phenanthrene) toward soils microorganisms (nitrifying bacteria) was evaluated in 50 different soils. The soil samples were collected from agricultural land in four regions of Poland with varying levels of industrialization (Slaskie, Dolnoslaskie, Podlaskie, and Lubelskie voievodeships). Soils were characterized for basic physicochemical properties (texture, organic matter content, pH(KCl), total nitrogen content, total sorption capacity) and the content of contaminants including PAHs (73-800 microg kg(-1)), Pb (6-720 mg kg(-1)), and Zn (9-667 mg kg(-1)). Ecotoxicity of phenanthrene (applied at 10, 100, 500, and 1000 mg kg(-1)) to soils microorganisms was evaluated in laboratory studies in control conditions (incubation of soils for 7 d at 20 +/- 2 degrees C). Nitrification potential was used as the ecotoxicity measurements end point. The EC50 values (146-1670 mg kg(-1)) calculated from the square root-X linear regression model differed significantly in various soils, although it was difficult to establish a causative relationship between soil physicochemical characteristic and phenanthrene toxicity. A significant factor in the assessment of soils vulnerability to the effect of phenanthrene was level of soil contamination, particularly with PAHs. Soils with previous contamination were more susceptible (mean EC50, 325 mg kg(-1)) than soils from uncontaminated, rural areas (mean EC50, 603 mg kg(-1)).     

Differential responses of eubacterial, Mycobacterium, and Sphingomonas communities in polycyclic aromatic hydrocarbon (PAH)-contaminated soil to artificially induced changes in PAH profile

Recent reports suggest that Mycobacterium is better adapted to soils containing poorly bioavailable polycyclic aromatic hydrocarbons (PAHs) compared to Sphingomonas. To study this hypothesis, artificial conditions regarding PAH profile and PAH bioavailability were induced in two PAH-contaminated soils and the response of the eubacterial, Mycobacterium, and Sphingomonas communities to these changed conditions was monitored during laboratory incubation. Soil K3663 with a relatively high proportion of high molecular weight PAHs was amended with phenanthrene or pyrene to artificially change the soil into a soil with a relatively increased bioavailable PAH contamination. Soil AndE with a relatively high proportion of bioavailable low molecular weight PAHs was treated by a single-step Tenax extraction to remove the largest part of the easily bioavailable PAH contamination. In soil K3663, the added phenanthrene or pyrene compounds were rapidly degraded, concomitant with a significant increase in the number of phenanthrene and pyrene degraders, and minor and no changes in the Mycobacterium community and Sphingomonas community, respectively. However, a transient change in the eubacterial community related to the proliferation of several gamma-proteobacteria was noted in the phenanthrene-amended soil. In the extracted AndE soil, the Sphingomonas community initially developed into a more diverse community but finally decreased in size below the detection limit. Mycobacterium in that soil never increased to a detectable size, while the eubacterial community became dominated by a gamma-proteobacterial population. The results suggest that the relative bioavailability of PAH contamination in soil affects bacterial community structure but that the behavior of Mycobacterium and Sphingomonas in soil is more complex than prospected from studies on their ecology and physiology.     

Comparison of plant families in a greenhouse phytoremediation study on an aged polycyclic aromatic hydrocarbon-contaminated soil

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous, recalcitrant, and potentially carcinogenic pollutants. Plants and their associated rhizosphere microbes can promote PAH dissipation, offering an economic and ecologically attractive remediation technique. This study focused on the effects of different types of vegetation on PAH removal and on the interaction between the plants and their associated microorganisms. Aged PAH-polluted soil with a total PAH level of 753 mg kg(-1) soil dry weight was planted with 18 plant species representing eight families. The levels of 17 soil PAHs were monitored over 14 mo. The size of soil microbial populations of PAH degraders was also monitored. Planting significantly enhanced the dissipation rates of all PAHs within the first 7 mo, but this effect was not significant after 14 mo. Although the extent of removal of lower-molecular-weight PAHs was similar for planted and unplanted control soils after 14 mo, the total mass of five- and six-ring PAHs removed was significantly greater in planted soils at the 7- and 14-mo sampling points. Poaceae (grasses) were the most effective of the families tested, and perennial ryegrass was the most effective species; after 14 mo, soils planted with perennial ryegrass contained 30% of the initial total PAH concentration (compared with 51% of the initial concentrations in unplanted control soil). Although the presence of some plant species led to higher populations of PAH degraders, there was no correlation across plant species between PAH dissipation and the size of the PAH-degrading population. Research is needed to understand differences among plant families for stimulating PAH dissipation.     

Soil-to-root transfer and translocation of polycyclic aromatic hydrocarbons by vegetables grown on industrial contaminated soils

Polycyclic aromatic hydrocarbons (PAHs) are possible contaminants in some former industrial sites, representing a potential risk to human health if these sites are converted to residential areas. This work was conducted to determine whether PAHs present in contaminated soils are transferred to edible parts of selected vegetables. Soils were sampled from a former gasworks and a private garden, exhibiting a range of PAH concentrations (4 to 53 to 172 to 1263 and 2526 mg PAHs kg-1 of dry soil), and pot experiments were conducted in a greenhouse with lettuce (Lactuca sativa L. var. Reine de Mai), potato (Solanum tuberosum L. var. Belle de Fontenay), and carrot (Daucus carota L. var. Nantaise). At harvest, above- and below ground biomass were determined and the PAH concentrations in soil were measured. In parallel, plates were placed in the greenhouse to estimate the average PAH-dust deposition. Results showed that the presence of PAHs in soils had no detrimental effect on plant growth. Polycyclic aromatic hydrocarbons were detected in all plants grown in contaminated soils. However, their concentration was low compared with the initial soil concentration, and the bioconcentration factors were low (i.e., ranging from 13.4 x 10(-4) in potato and carrot pulp to 2 x 10(-2) in potato and carrot leaves). Except in peeled potatoes, the PAH concentration in vegetables increased with the PAH concentration in soils. The PAH distribution profiles in plant tissues and in soils suggested that root uptake was the main pathway for high molecular weight PAHs. On the opposite, lower molecular weight PAHs were probably taken up from the atmosphere through the leaves as well as by roots.     

H(+)/phenanthrene symporter and aquaglyceroporin are implicated in phenanthrene uptake by wheat (Triticum aestivum L.) roots

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic pollutants that are toxic to human and nonhuman organisms. Dietary intake of PAHs is a dominant route of exposure for the general population because food crops are a major source of dietary PAHs. The mechanism for crop root uptake of PAHs remains unclear. Here we reveal that wheat root uptake of PAHs involves active and passive processes. The passive uptake is mercury and glycerol dependent. Mercury and glycerol inhibit uptake, indicating that aquaglyceroporins sensitive to mercury contribute to passive uptake. Active uptake is mediated by a phenanthrene/H symporter. The electrical response of wheat roots triggered by phenanthrene consists of two sequential phases: depolarization followed by repolarization. The depolarization is phenanthrene concentration dependent, with saturation kinetics that have an apparent of K(m) 10.8 μmol L(-1). As uptake proceeds, external solution pH increase is noticed. Lower pH favors the uptake. Vanadate and 2,4-dinitrophenol suppress the electrical response to phenanthrene and phenanthrene uptake, suggesting that plasma membrane H(+)-ATPase is involved in the establishment of an electrochemical proton gradient acting as a driving force for active uptake. Therefore, it is suggested that aquaglyceroporin and phenanthrene/H symporter are implicated in phenanthrene uptake. Our results provide insight into PAH uptake mechanism in wheat roots that is relevant to strategies for reducing PAH accumulation in wheat for food safety, improving phytoremediation of PAH-contaminated soils or water by agronomic practices and genetic modification to target remedial plants for higher PAH uptake capacity.     

Effects of agronomic practices on phytoremediation of an aged PAH-contaminated soil

Phytoremediation offers an ecologically and economically attractive remediation technique for soils contaminated with polycyclic aromatic hydrocarbons (PAHs). In addition to the choice of plant species, agronomic practices may affect the efficiency of PAH phytoremediation. Inorganic nutrient amendments may stimulate plant and microbial growth, and clipping aboveground biomass might stimulate root turnover, which has been associated with increases in soil microbial populations. To assess the influence of fertilization and clipping on PAH dissipation in a nutrient-poor, aged PAH-contaminated soil, a 14-mo phytoremediation study was conducted using perennial ryegrass (Lolium perenne) as a model species. Six soil treatments were performed in replicate: unplanted; unplanted and fertilized; planted; planted and fertilized; planted and clipped; and planted, clipped, and fertilized. Plant growth, soil PAH concentrations, and the concentrations of total and PAH-degrading microorganisms were measured after 7 and 14 mo. Overall, planting (with nearly 80% reduction in total PAHs) and planting + clipping (76% reduction in total PAHs) were the most effective treatments for increased PAH dissipation after 14 mo. Fertilization greatly stimulated plant and total microbial growth, but negatively affected PAH dissipation (29% reduction in total PAHs). Furthermore, unplanted and fertilized soils revealed a similar negative impact (25% reduction) on PAH dissipation after 14 mo. Clipping did not directly affect PAH dissipation, but when combined with fertilization (61% reduction in total PAHs), appeared to mitigate the negative impact of fertilization on PAH dissipation. Therefore, fertilization and clipping may be included in phytoremediation design strategies, as their combined effect stimulates plant growth while not affecting PAH dissipation.     

9,10-Phenanthrenequinone photoautocatalyzes its formation from phenanthrene, and inhibits biodegradation of naphthalene

Polycyclic aromatic hydrocarbons (PAHs) have earned considerable attention due to their widespread environmental distribution and toxicity. In the environment, PAHs decompose by a variety of biotic and abiotic pathways. In both polar and nonpolar environments, phenanthrene (Phe, a common, three-ring PAH) is converted by sunlight to more polar products such as 9,10-phenanthrenequinone (PheQ) and subsequent oxidation products such as the corresponding open-ring dicarboxylic acid product. Biodegradation of phenanthrene also usually leads to oxidative metabolites, and eventually ends in mineralization. Our experimental objective was to investigate the photodegradation of phenanthrene and determine the effect of reaction products such as PheQ on microbial biodegradation of two- and three-ring PAHs. Abiotic experiments were performed to examine the photolytic breakdown of Phe; Phe was converted to PheQ, which catalyzed its own formation. In biodegradation experiments PheQ (0.04-4 mg/L) caused marked inhibition of naphthalene (Nap) biodegradation by a Burkholderia species; Phe did not. Only 20% of the naphthalene was degraded in the presence of PheQ compared with 75% in the control culture with no PheQ added. No PAH-degrading cultures were able to use PheQ as sole carbon source; however, the Phe-degrading enrichment culture dominated by a Sphingomonas species was able to degrade PheQ cometabolically in the presence of Phe. These results may explain why photooxidized phenanthrene-containing mixtures can resist biodegradation.     

Polycyclic aromatic hydrocarbons in mountain soils of the subtropical Atlantic

Surface soil samples from various altitudes on Tenerife Island, ranging from sea level up to 3400 m above mean sea level, were analyzed to study the distribution of 26 polycyclic aromatic hydrocarbons (PAHs) in a remote subtropical area. The stable atmospheric conditions in this island define three vertically stratified layers: marine boundary, trade-wind inversion, and free troposphere. Total PAH concentrations, 1.9 to 6000 microg/kg dry wt., were high when compared with those in tropical areas and in a similar range to those in temperate areas. In the marine boundary layer, fluoranthene (Fla), pyrene (Pyr), benz [a]anthracene (BaA), and chrysene (C + T) were largely dominant. The predominance of Fla over Pyr may reflect photo-oxidative processes during atmospheric transport, although coal combustion inputs cannot be excluded. The PAHs found in higher concentration in the soils from the inversion layer were benzo[b + j]fluoranthene (BbjF) + benzo[k]fluoranthene (BkF) > benzo[e]pyrene (BeP) approximately indeno[1,2, 3-cd]pyrene (Ind) > benzo[a]pyrene (BaP) approximately benzo[ghi]perylene (Bghi) > coronene (Cor) approximately dibenz[a,h]anthracene (Dib), reflecting that high temperatures and insolation prevent the accumulation of PAHs more volatile than BbjF in significant amounts. These climatic conditions involve a process of standardization that prevents the identification of specific PAH sources such as traffic, forest fires, or industrial inputs. Only soils with high total organic carbon (TOC) (e.g., 10-30%) preserve the more volatile compounds such as phenanthrene (Phe), methylphenanthrenes (MPhe), dimethylphenanthrenes (DMPhe), and retene (Ret). However, no relation between PAHs and soil TOC and black carbon (BC) was found. The specific PAH distributions of the free tropospheric region suggest a direct input from pyrolytic processes related to the volcanic emission of gases in Teide.     

Sequential supercritical fluid extraction (SSFE) for estimating the availability of high molecular weight polycyclic aromatic hydrocarbons in historically polluted soils

Sequential supercritical fluid (CO2) extraction (SSFE) was applied to eight historically contaminated soils from diverse sources with the aim to elucidate the sorption-desorption behavior of high molecular weight polycyclic aromatic hydrocarbons (PAHs). The method involved five extraction phases applying successively harsher conditions by increasing fluid temperature and density mobilizing target compounds from different soil particle sites. Two groups of soils were identified based on readily desorbing (available) PAH fractions obtained under mildest extraction conditions (e.g., readily desorbing fractions of fluoranthene and pyrene significantly varied between the soils ranging from <10 to >90%). Moreover, extraction behavior strongly correlated with molecular weight revealing decreasing available PAH fractions with increasing weight. Physicochemical soil parameters such as particle size distribution and organic dry mass were found to have no distinct effect on the sorption-desorption behavior of PAHs in the different soils. However, PAH profiles significantly correlated with readily available pollutant fractions; soils with relatively less mobile PAHs had higher proportions of five- and six-ring PAHs and vice versa. Eventually, biodegradability corresponded well with PAH recoveries under the two mildest extraction phases. However, a quantitative relationship was only established for soils with biodegradable PAHs. Out of eight soils, five showed no biodegradation including the four soils with the lowest fraction of readily desorbing PAHs. Only one soil (which was found to be highly toxic to Vibrio fischeri) did not match the overall pattern showing no PAH biodegradability but large fractions of highly mobile PAHs, concluding that mass transfer limitations may only be one of many factors governing biodegradability of PAHs.     

Effect of electrokinetics on the bioaccessibility of polycyclic aromatic hydrocarbons in polluted soils

Bioaccessibility is one of the most relevant aspects to be considered in the restoration of soils using biological technologies. Polycyclic aromatic hydrocarbons (PAH) usually have residual fractions that are resistant to biodegradation at the end of the biological treatment. In some situations, these residual concentrations could still be above legal standards. Here, we propose that the available knowledge about electroremediation technologies could be applied to enhance bioremediation of soils polluted with PAH. The main objective of this study was to show that a previous electrokinetic treatment could reduce the PAH residual fractions when the soil is subsequently treated by means of a bioremediation process. The approach involved the electrokinetic treatment of PAH-polluted soils at a potential drop of 0.9 to 1.1 V/cm and the subsequent estimations of bioaccessibility of residual PAHs after slurry-phase biodegradation. Bioaccessibility of PAH in two creosote-polluted soils (clay and loamy sand, total PAH content averaging 300 mg/kg) previously treated with an electric field in the presence of nonionic surfactant Brij 35 was often higher than in untreated controls. For example, total PAH content remaining in clay soil after bioremediation was only 62.65 +/- 4.26 mg/kg, whereas a 7-d electrokinetic pretreatment had, under the same conditions, a residual concentration of 29.24 +/- 1.88 mg/kg after bioremediation. Control treatments without surfactant indicated that the electrokinetic treatment increased bioaccessibility of PAHs. A different manner of electric field implementation (continuous current vs. current reversals) did not induce changes in PAH bioaccessibility. We suggest that this hybrid technology may be useful in certain bioremediation scenarios, such as soils rich in clay and black carbon, which show limited success due to bioavailability restrictions, as well as in highly heterogeneous soils.     

Polycyclic aromatic hydrocarbon release from a soil matrix in the in vitro gastrointestinal tract

Soil ingestion is an important exposure route by which immobile soil contaminants enter the human body. We assessed polycyclic aromatic hydrocarbon (PAH) release from a contaminated soil, containing 49 mg PAH kg(-1), using a SHIME (Simulator of the Human Intestinal Microbial Ecosystem) reactor comprising the stomach, duodenal, and colon compartments. Polycyclic aromatic hydrocarbon release was defined as that fraction remaining in the digest supernatant after centrifugation for 5 min at 1500 x g. The PAH release in the stomach digest was only 0.44% of the total PAH present in soil, resulting in PAH concentrations of 23 micrograms PAH L(-1) chyme. The lower PAH releases in duodenum (0.13%) and colon (0.30%) digests, compared with the stomach digest, were thought to be attributed to combined complexation and precipitation with bile salts, dissolved organic matter, or colon microbiota. We studied these complexation processes in an intestinal suspension more in depth by preparing mixtures of 9-anthracenepropionic acid, a Bacillus subtilis culture, and cholin as model compounds for PAHs, organic matter, and bile salts, respectively. Bile salts or organic matter in the aqueous phase initially enhance PAH desorption from soil. However, desorbed PAHs may form large aggregates with bile and organic matter, lowering the freely dissolved PAH fraction in the supernatant. Using the model compounds, mathematical equations were developed and validated to predict PAH complexation processes in the gastrointestinal tract. Contaminant release and subsequent complexation in the gut is an important prerequisite to intestinal absorption and thus bioavailability of that contaminant. The data from this research may help in understanding the processes to which PAHs are subjected in the gastrointestinal tract, before intestinal absorption.     

Depolymerization of polyaromatic hydrocarbons by Penicillium spp. inhabit the phyllosphere of urban ornamental plants

A variety of anthropogenic sources release hazardous polyaromatic hydrocarbons (PAHs) into the phyllosphere which is an excellent niche for diverse fungi, and some of them have PAHs degradation capabilities. Therefore, this research attempted to determine the PAHs (phenanthrene, anthracene, naphthalene, and pyrene) degradation capability of phyllosphere inhabited Penicillium species. The leaf samples were collected from highly polluted urban areas (Panchikawatta, Pettah, Orugodawatta, Maradana, Sapugaskanda, and Colombo Fort) in Sri Lanka to isolate fungal species inhabiting the phyllosphere. Furthermore, their distribution patterns among the leaf tissue layers were studied using bright-field microscopic observations. Moreover, the best PAH degraders were screened out using plate assays and confirmed through High Performance Liquid Chromatography (HPLC) analysis. Further, their enzymatic activities during the PAHs degradation were analyzed. As per the microscopic observations, the highest fungal distribution was in the upper epidermis of the leaves followed by the fungal distribution in the interspaces of palisade mesophyll layers. Out of isolated fungal species, two Penicillium spp. (Penicillium citrinum P₂₃B-91 and Penicillium griseofulvum P₉B - 30) showed the highest PAHs (phenanthrene, anthracene, naphthalene, and pyrene) degradation capabilities. Manganese peroxidase (MnP) enzyme dominated phenanthrene degradation in P. griseofulvum P₉B - 30, which showed the highest phenanthrene degradation ability (61%). In addition, P. citrinum P23B-91 was good at degrading anthracene (88%) and also displayed a higher MnP activity during the anthracene degradation than laccase and lignin peroxidase activities. The discoveries from the toxicity assay during the PAHs degradation processes revealed that the produced byproducts had no toxic effects on the fungal growth cycle and the phyllosphere. Therefore this phyllosphere Penicillium spp. are ideal for the bioremediation of polluted air in urbanized areas.     

Polycyclic aromatic hydrocarbon removal from soil by surfactant solubilization and Phanerochaete chrysosporium oxidation

Surfactant soil washing can remove polycyclic aromatic hydrocarbons (PAHs) from contaminated soil, and the white rot fungus, Phanerochaete chrysosporium Burdsall in Burdsall & Eslyn, can oxidize PAHs. The objective of this study was to develop a novel bioremediation technology using a combination of abiological surfactant soil washing followed by PAH biological oxidation in soil washwater using P. chrysosporium in a rotating biological contactor (RBC) reactor. Soil used for experimentation was an 11-month aged contaminated soil spiked with a total of nine PAHs: acenaphthene, fluorene, phenanthrene, fluoranthene, pyrene, chrysene, benzo(a)pyrene, dibenz(a-h)anthracene, and benzo(ghi)perylene. After 11 months of aging, recovery percentages of high molecular weight PAHs [i.e., from chrysene to benzo(ghi)perylene] were greater than 86%, while those of low molecular weight PAHs (i.e., from acenaphthene to pyrene) were less than 19%. Total removal efficiency for any of the nine PAHs was greater than 90% using a combination of surfactant soil washing and P. chrysosporium oxidation of soil washwater in the RBC reactor when used in batch operation, and greater than 76% when used in continuous operation. The treatment of PAH-contaminated soil using a combination of surfactant soil washing and subsequent PAH removal from the resultant washwater in an RBC reactor, in the presence of immobilized P. chrysosporium, permits (i) a rapid abiological cleanup of soil for compliance with relevant soil quality standards and (ii) PAH biological removal in soil washwater for compliance with aqueous discharge standards.     

Sequential accelerated solvent extraction of polycyclic aromatic hydrocarbons with different solvents: performance and implication

Sixteen USEPA priority polycyclic aromatic hydrocarbons (PAHs) extracted by Soxhlet extraction (S-PAHs) with dichloromethane and routine accelerated solvent extraction (A-PAHs) with 1:1 toluene/methanol, respectively, were investigated in 24 soil samples from two cities in the center of the Pearl River Delta, South China. Polycyclic aromatic hydrocarbons, methylphenanthrene and perylene, in two soils, two sediments, and an immature oil shale were also sequentially extracted by accelerated solvent extraction (ASE) with each of four different organic solvents for three times. The A-PAHs' concentrations are 2.41 times the S-PAHs' concentrations. For sequential three ASEs, PAHs in the first extract account for 56 to 67% of their total concentrations in the sequential three extractions and toluene displays the best extraction performance among the four solvents. Diagnostic ratios of PAHs in Soxhlet extraction, routine ASE, and sequential ASE with each solvent for a given sample are very similar, suggesting their identical petrogenic and pyrogenic sources in the soils and sediments. But the PAH ratios for the shale have an obvious petrogenic origin. The perylene/5-ring PAH ratios indicate a diagenetic source, especially in the shale and sediments. The correlation analysis shows that A-PAHs/S-PAHs is better associated with the contents of total organic carbon (TOC) than those of black carbon (BC). The above results indicate the significant petrogenic origin of PAHs and the important effect of organic matter on their extraction and distribution in the investigated field soils/sediments.     

Forest fertilization with wood ash: effect on the distribution and storage of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs)

Before wood ash can be safely used as a fertilizer in forests, possible negative effects such as input of organic contaminants or remobilization of contaminants already stored in the soil must be investigated. The objective of this study was to examine the effects of wood ash application on concentrations, storage, and distribution of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in a Swiss forest soil. In May 1998, we added 8 Mg wood ash ha(-1) to a forest soil. We determined 20 PAHs and 14 PCBs in the organic layer, in the bulk mineral soil, and in soil material taken from preferential flow paths and from the matrix before and after the wood ash application. In the control plots, the concentrations of PAHs in the organic layer indicated moderate pollution (sum of 20 PAHs: 0.8-1.6 mg kg(-1)), but sum of PCB concentrations was high (21-48 microLg kg(-1)). The wood ash had high concentrations of PAHs (sum of 20 PAHs: 16.8 mg kg(-1)), but low concentrations of PCBs (sum of 14 PCBs: 3.4 microg kg(-1)). The wood ash application increased the PAH concentrations in the organic horizons up to sixfold. In contrast, PCB concentrations did not change in the Oa horizon and decreased up to one third in the Oi and Oe horizons. The decrease was probably caused by the mobilization of stored PCBs because of the high pH of the wood ash. This probably results in a higher mobility of dissolved organic matter, acting as PCB carrier. In the mineral soil, the preferential flow paths of the A horizon contained more PAHs and PCBs (+20 +/- 15% and +43 +/- 60%, respectively) than the matrix. This was particularly true for higher molecular weight compounds (molecular weight > 200 g mol(-1)). Below 50 cm depth, concentrations of PAHs and PCBs were smaller in the preferential flow paths, suggesting that in deeper depths, processes acting as sinks dominated over inputs in the preferential flow paths.     

Removal of polycyclic aromatic hydrocarbons from aqueous solution on soybean stalk-based carbon

Soybean [ (L.) Merr.] stalk-based carbons were prepared by phosphoric acid activation at different carbonization temperatures. Characteristics of the prepared carbon, including specific surface area, iodine number, and amount of methylene blue sorption, were determined. Experiments on phenanthrene, naphthalene, and acenaphthene, as representatives of polycyclic aromatic hydrocarbons (PAHs), removal from aqueous solution by the prepared carbon were conducted at different levels of carbon addition. The results indicated that the specific surface area, iodine number, and amount of methylene blue sorption increased with an increase of carbonization temperature. The maximum values were observed at 700°C and were 287.63 m g, 508.99 mg g, and 90.14 mg g, respectively. The removal efficiencies of phenanthrene, naphthalene, and acenaphthene tended to increase with increasing carbon amounts and carbonization temperature. The optimal removal performance was obtained under the experimental conditions of carbon concentrations of 0.04 g 32 mL and carbonization temperature of 700°C, and the removal efficiencies of phenanthrene, naphthalene, and acenaphthene were 99.89, 100, and 95.64%, respectively. The performance of the prepared carbon was superior to that of commercial activated carbon. Additionally, for the same carbon concentrations, the removal efficiency of PAHs on prepared carbons followed the order: phenanthrene > naphthalene > acenaphthene. Results obtained from this work provide some insight into the reuse of an agricultural residue, and also provide a new application for the treatment of PAHs in contaminated water utilizing activated carbon prepared from agricultural residues.     

Integrating biodegradation and electroosmosis for the enhanced removal of polycyclic aromatic hydrocarbons from creosote-polluted soils

This paper presents a hybrid technology of soil remediation based on the integration of biodegradation and electroosmosis. We employed soils with different texture (clay soil and loamy sand) containing a mixture of polycyclic aromatic hydrocarbons (PAH) present in creosote, and inoculation with a representative soil bacterium able to degrade fluorene, phenanthrene, fluoranthene, pyrene, anthracene, and benzo[a]pyrene. Two different modes of treatment were prospected: (i) inducing in soil the simultaneous occurrence of biodegradation and electroosmosis in the presence of a biodegradable surfactant, and (ii) treating the soils sequentially with electrokinetics and bioremediation. Losses of PAH due to simultaneous biodegradation and electroosmosis (induced by a continuous electric field) were significantly higher than in control cells that contained the surfactant but no biological activity or no current. The method was especially successful with loamy sand. For example, benzo[a]pyrene decreased its concentration by 50% after 7 d, whereas 22 and 17% of the compound had disappeared as a result of electrokinetic flushing and bioremediation alone, respectively. The use of periodical changes in polarity and current pulses increased by 16% in the removal of total PAH and in up to 30% of specific compounds, including benzo[a]pyrene. With the aim of reaching lower residual levels through bioremediation, an electrokinetic pretreatment was also evaluated as a way to mobilize the less bioaccessible fraction of PAH. Residual concentrations of total biodegradable PAH, remaining after bioremediation in soil slurries, were twofold lower in electrokinetically pretreated soils than in untreated soils. The results indicate that biodegradation and electroosmosis can be successfully integrated to promote the removal of PAH from soil.     

Characterization of slow pyrolysis biochars: effects of feedstocks and pyrolysis temperature on biochar properties

Biochars are increasingly used as soil amendment and for C sequestration in soils. The influence of feedstock differences and pyrolysis temperature on biochar characteristics has been widely studied. However, there is a lack of knowledge about the formation of potentially toxic compounds that remain in the biochars after pyrolysis. We investigated biochars from three feedstocks (wheat straw, poplar wood, and spruce wood) that were slowly pyrolyzed at 400, 460, and 525°C for 5 h (straw) and 10 h (woodchips), respectively. We characterized the biochars' pH, electrical conductivity, elemental composition (by dry combustion and X-ray fluorescence), surface area (by N adsorption), water-extractable major elements, and cation exchange capacity (CEC). We further conducted differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffractometry to obtain information on the biochars' molecular characteristics and mineralogical composition. We investigated trace metal content, total polycyclic aromatic hydrocarbon (PAH) content, and PAH composition in the biochars. The highest salt (4.92 mS cm) and ash (12.7%) contents were found in straw-derived biochars. The H/C ratios of biochars with highest treatment temperature (HTT) 525°C were 0.46 to 0.40. Surface areas were low but increased (1.8-56 m g) with increasing HTT, whereas CEC decreased (162-52 mmol kg) with increasing HTT. The results of DSC and FTIR suggested a loss of labile, aliphatic compounds during pyrolysis and the formation of more recalcitrant, aromatic constituents. X-ray diffractometry patterns indicated a mineralogical restructuring of biochars with increasing HTT. Water-extractable major and trace elements varied considerably with feedstock composition, with trace elements also affected by HTT. Total PAH contents (sum of EPA 16 PAHs) were highly variable with values up to 33.7 mg kg; irrespective of feedstock type, the composition of PAHs showed increasing dominance of naphthalene with increasing HTT. The results demonstrate that biochars are highly heterogeneous materials that, depending on feedstock and HTT, may be suitable for soil application by contributing to the nutrient status and adding recalcitrant C to the soil but also potentially pose ecotoxicological challenges.