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.     

Availability of arsenic, copper, lead, thallium, and zinc to various vegetables grown in slag-contaminated soils

To anticipate a possible hazard resulting from the plant uptake of metals from slag-contaminated soils, it is useful to study whether vegetables exist that are able to mobilize a given metal in the slag to a larger proportion than in an uncontaminated control soil. For this purpose, we studied the soil to plant transfer of arsenic, copper, lead, thallium, and zinc by the vegetables bean (Phaseolus vulgaris L. 'dwarf bean Modus'), kohlrabi (Brassica oleracea var. gongylodes L.), mangold (Beta vulgaris var. macrorhiza ), lettuce (Lactuca sativa L. 'American gathering brown'), carrot (Daucus carota L. 'Rotin', 'Sperlings's'), and celery [Apium graveiolus var. dulce (Mill.) Pers.] from a control soil (Ap horizon of a Entisol) and from a contaminated soil (1:1 soil-slag mixtures). Two types of slags were used: an iron-rich residue from pyrite (FeS2) roasting and a residue from coal firing. The metal concentrations in the slags, soils, and plants were used to calculate for each metal and soil-slag mixture the plant-soil fractional concentration ratio (CRfractional,slag), that is, the concentration ratio of the metal that results only from the slag in the soil. With the exception of TI, the resulting values obtained for this quantity for As, Cu, Pb, and Zn and for all vegetables were significantly smaller than the corresponding plant-soil concentration ratios (CRcontrol soil) for the uncontaminated soil. The results demonstrate quantitatively that the ability of a plant to accumulate a given metal as observed for a control soil might not exist for a soil-slag mixture, and vice versa.     

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.     

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.     

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.     

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.     

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.     

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.     

Polycyclic aromatic hydrocarbons (PAHs) in soils of the Moscow Region--concentrations, temporal trends, and small-scale distribution

The knowledge of the environmental fate of polycyclic aromatic hydrocarbons (PAHs) is restricted to few climatic regions of the world almost excluding the Taiga. Our objectives were to (i) separate anthropogenic from background contributions to PAH concentrations and (ii) determine temporal trends in PAH concentrations during the last century including the change in distribution of PAHs in interior and exterior portions of aggregates in soils of the Moscow region. Along a southeast-bound transect from Moscow (windward in winter) and at a background location northeast of Moscow (leeward in winter), seven topsoil samples were collected in 1910-1954 and 35 in 1998-2003. We fractionated the soils in interior and exterior portions of aggregates > 10 mm and remaining soil without aggregates. The sum of 21 PAHs (sigma21PAHs) concentrations in recent bulk soil ranged from 59 to 1350 ng g(-1). The concentrations of all PAHs were lower outside than in Moscow. The range of the concentrations of the sigma21PAHs in archived soil samples (159-1280 ng g(-1)) was similar as in recent soils. In most recent and archived samples, naphthalene and phenanthrene, were most abundant. The concentrations of low-molecular-weight PAHs decreased during the last century at most sites; those of high-molecular-weight compounds increased. The sigma21PAHs concentrations were accumulated in the exterior of aggregates (109%) and depleted in the interior (95%) relative to the concentration in bulk soil (defined as 100%), which was similar to that in the soil without aggregates (99%). The differences between aggregate interior and exterior did not change during the last century. The dominance of naphthalene and phenanthrene is typical of remote regions. The urban influence on PAH concentrations in the last century was small.     

Genotoxicity is unrelated to total concentration of priority carcinogenic polycyclic aromatic hydrocarbons in soils undergoing biological treatment

A solid-phase microbiological assay was used to determine the changes in genotoxicity associated with sequestration or biodegradation of carcinogenic compounds in contaminated soils. The concentration of six carcinogenic polycyclic aromatic hydrocarbons (PAHs) did not change in 59 d in sterile soil, but the genotoxicity declined markedly. In a soil undergoing bioremediation in the field for 147 d or biodegradation in the laboratory for 180 d, the concentrations either changed little or declined at different rates, but the genotoxicity increased followed by a decline. The genotoxicity of a second soil declined as a result of biological treatment. The data show that genotoxicity of contaminated soils may be unrelated to the concentration of carcinogenic PAHs because of aging or new mutagens formed during biological treatment.     

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.     

Effect of root death and decay on dissipation of polycyclic aromatic hydrocarbons in the rhizosphere of yellow sweet clover and tall fescue

A 12-mo greenhouse study was conducted to evaluate the contribution of root death and decay on the dissipation of polycyclic aromatic hydrocarbons (PAHs) in rhizosphere soil. The contaminated soil was previously treated by land-farming, but residual PAHs remained after treatment. Tall fescue (Festuca arundinacea Schreb.) and yellow sweet clover (Melilotus officinalis Lam.) were the target plants. To specifically evaluate the effect of root decay on contaminant dissipation, plants were treated with glyphosate, a broad spectrum herbicide, to induce root decay. Although tall fescue treatments had the highest root and shoot biomass and root surface area, this plant did not result in the highest contaminant degradation rates. Significant differences were noted between treatments for seven PAHs, with the active yellow sweet clover resulting in 60 to 75% degradation of these compounds. Induced root death and decay did not produce a significant enhancement of PAH degradation. The PAH microbial degrader populations in the vegetated treatments were more than 100 times greater than those in the unvegetated control. The phospholipid fatty acid (PLFA) structural group profile shifted over the growing period, indicating a change in the community structure. In conclusion, phytoremediation was shown to be an effective polishing tool for PAH-affected soil previously subjected to biological treatment.     

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.     

Arsenic availability from chromated copper arsenate (CCA)-treated wood

Lumber used to construct raised garden beds is often treated with chromated copper arsenate (CCA). This project aimed to determine (i) how far As, Cu, and Cr had diffused away from CCA-treated wood surfaces in raised garden beds under realistic conditions, (ii) the uptake of these elements by crops, and (iii) the effect of CCA solution on soil bacteria. This study showed that As, Cu, and Cr diffuse into soil from CCA-treated wood used to construct raised garden beds. To determine crop uptake of these elements, contaminated soil 0 to 2 cm from the treated wood was obtained from two different beds (40-50 mg kg(-1) As); control soil was collected 1.5 m away from the treated wood (<3-10 mg kg(-1) As). Four replicates of carrot (Daucus carota var. sativus Hoffm. cv. Thumbelina), spinach (Spinacia oleracea L. cv. Indian Summer), bush bean (Phaseolus vulgaris L. cv. Provider), and buckwheat (Fagopyrum esculentum Moench cv. Common) were grown in pots containing these soils in a greenhouse. After harvest, plant materials were dried, ground, digested, and analyzed for As by inductively coupled plasma-hydride generation (ICP-HG). Concentrations of As in all crops grown in contaminated soils were higher than those from control soils. The levels of As in the crops remained well below the recommended limit for As set by the United States Public Health Service (2.6 mg kg(-1) fresh wt.). To determine if bacteria in soils 0 to 2 cm from the treated wood had higher resistance to Type C chromated copper arsenate (CCA-C) solution than those from reference soils, dilution plates were set up using quarter-strength tryptic soy agar (TSA) media and 0 to 22.94 g L(-1) (0-1.25% v/v) CCA-C working solution. The microorganisms from soils adjacent to treated wood had greater growth on the CCA-amended media than those from reference soils outside the bed.     

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.     

Food safety assessment of planting patterns of four vegetable-type crops grown in soil contaminated by electronic waste activities

A field experiment was conducted to assess the effect of crop and planting pattern on levels of cadmium (Cd), lead (Pb), and copper (Cu) in crops grown in soil contaminated by electronic waste. The crops were maize (Zea mays L. var. Shentian-1), tomato (Solanum lycopersicum L. var. Zhongshu-4), cabbage (Brassica oleracea L. var. Jingfeng-1), and pakchoi (Brassica chinensis (L.) Makino. var. Youdonger-Hangzhou). The planting patterns were crop monoculture, crop co-planted with a legume, and crop co-planted with another crop. Metal concentrations in the edible parts of the crops varied with types of metals and crops. Pb concentration was higher in leafy vegetables (cabbage and pakchoi) than in maize or tomato, Cd concentration was higher in tomato and pakchoi than in maize or cabbage, and Cu concentration was higher in maize and pakchoi than in tomato or cabbage. Metal concentrations in the edible part were also influenced by planting pattern. Relative to monoculture, co-planting and especially co-planting with Japanese clover tended to decrease Pb accumulation and increase Cd accumulation. According to the maximum permissible concentration (MPC) standard of the National Standard Agency in China, only maize (under all planting patterns) could be safely consumed. Because co-planting tended to increase Cd accumulation even in maize, however, the results suggest that maize monoculture is the optimal crop and planting pattern for this kind of contaminated soil.     

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.     

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)).     

Degradation of polycyclic aromatic hydrocarbons by combined chemical pre-oxidation and bioremediation in creosote contaminated soil

The ability of pre-oxidation to overcome polycyclic aromatic hydrocarbons (PAH) recalcitrance to biodegradation was investigated in creosote contaminated soil. Sand and peat artificially spiked with creosote (quality WEI C) were used as model systems. Ozonation and Fenton-like treatment were proved to be feasible technologies for PAH degradation in soil. The efficiency of ozonation was strongly dependent on the water content of treated soil samples. The removal of PAH by Fenton-like treatment depended on the applied H2O2/soil weight ratio and ferrous ions addition. It was determined that the application of chemical oxidation in sand resulted in a higher PAH removal and required lower oxidant (ozone, hydrogen peroxide) doses. The enhancement of PAH biodegradability by different pre-treatment technologies also depended on the soil matrix. It was ascertained that combined chemical and biological treatment was more efficient in PAH elimination in creosote contaminated soil than either one alone. Thus, the combination of Fenton-like and the subsequent biological treatment resulted in the highest removal of PAH in creosote contaminated sand, and biodegradation with pre-ozonation was found to be the most effective technology for PAH elimination in peat.     

A critical appraisal of PAH indices as indicators of PAH source and composition in Elelenwo Creek,southern Nigeria

The survey of polycyclic aromatic hydrocarbons (PAHs) and their relation to potential pollution sources were investigated in suspended particulate matter (SPM), surface waters, and sediments from Elelenwo Creek, southern Nigeria. Total PAH concentrations varied from 2,021.35 to 3,926.84 μg/kg dry weights in SPM and from 4,238.00 to 5,490.84 μg/kg dry weights in sediments. Furthermore, concentration levels of PAHs varied from 720.46 to 857.65 μg/l in the surface waters, which indicates that the aquatic ecosystem is polluted by PAHs. The 2, 3-ring PAHs were not dominant in SPM (34.73%), surface water (40.09%), and sediments (22.43%). While anthracene was more abundant, of the 2, 3-ring PAHs in SPM, the most abundant in the surface waters and sediments were fluorene and acenaphthylene. Four origin indices or concentration ratios of PAH isomer pairs were used to evaluate the suitability of these compounds as tracers to distinguish between the contamination arising from different sources. A critical appraisal of the PAH indices, therefore, suggested that biomass combustion is the major PAH source in the environmental matrices. Relative PAH patterns in the environmental matrices were also evaluated using principal component analysis, and were found to correlate with the PAH patterns of the different potential contamination sources.