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.     

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)).     

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.     

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.     

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.     

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.     

Soil carbon storage in silvopasture and related land-use systems in the brazilian cerrado

Silvopastoral management of fast-growing tree plantations is becoming popular in the Brazilian Cerrado (savanna). To understand the influence of such systems on soil carbon (C) storage, we studied C content in three aggregate size classes in six land-use systems (LUS) on Oxisols in Minas Gerais, Brazil. The systems were a native forest, a treeless pasture, 24- and 4-yr-old eucalyptus ( sp.) plantations, and 15- and 4-yr-old silvopastures of fodder grass plus animals under eucalyptus. From each system, replicated soil samples were collected from four depths (0-10, 10-20, 20-50, and 50-100 cm), fractionated into 2000- to 250-, 250- to 53-, and <53-μm size classes representing macroaggregates, microaggregates, and silt + clay, respectively, and their C contents determined. Macroaggregate was the predominant size fraction under all LUS, especially in the surface soil layers of tree-based systems. In general, C concentrations (g kg soil) in the different aggregate size fractions did not vary within the same depth. The soil organic carbon (SOC) stock (Mg C ha) to 1-m depth was highest under pasture compared with other LUS owing to its higher soil bulk density. The soils under all LUS had higher C stock compared with other reported values for managed tropical ecosystems: down to 1 m, total SOC stock values ranged from 461 Mg ha under pasture to 393 Mg ha under old eucalyptus. Considering the possibility for formation and retention of microaggregates within macroggregates in low management-intensive systems such as silvopasture, the macroaggregate dynamics in the soil seem to be a good indicator of its C storage potential.     

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.     

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.     

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.     

Pyrene degradation in forest humus microcosms with or without pine and its mycorrhizal fungus

The mineralization potential of forest humus and the self-cleaning potential of a boreal coniferous forest environment for polycyclic aromatic hydrocarbon (PAH) compounds was studied using a model ecosystem of acid forest humus (pH = 3.6) and pyrene as the model compound. The matrix was natural humus or humus mixed with oil-polluted soil in the presence and absence of Scots pine (Pinus sylvestris L.) and its mycorrhizal fungus (Paxillus involutus). The rates of pyrene mineralization in the microcosms with humus implants (without pine) were initially insignificant but increased from Day 64 onward to 47 microg kg(-1) d(-1) and further to 144 microg kg(-1) d(-1) after Day 105. In the pine-planted humus microcosms the rate of mineralization also increased, reaching 28 microg kg(-1) d(-1) after Day 105. The 14CO2 emission was already considerable in nonplanted microcosms containing oily soil at Day 21 and the pyrene mineralization continued throughout the study. The pyrene was converted to CO2 at rates of 0.07 and 0.6 microg kg(-1) d(-1) in the oily-soil implanted microcosms with and without pine, respectively. When the probable assimilation of 14CO2 by the pine and ground vegetation was taken into account the most efficient microcosm mineralized 20% of the 91.2 mg kg(-1) pyrene in 180 d. The presence of pine and its mycorrhizal fungus had no statistically significant effect on mineralization yields. The rates of pyrene mineralization observed in this study for forest humus exceeded the total annual deposition rate of PAHs in southern Finland. This indicates that accumulation in forest soil is not to be expected.     

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.     

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.     

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.     

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.     

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.     

Carbon storage by urban soils in the United States

We used data available from the literature and measurements from Baltimore, Maryland, to (i) assess inter-city variability of soil organic carbon (SOC) pools (1-m depth) of six cities (Atlanta, Baltimore, Boston, Chicago, Oakland, and Syracuse); (ii) calculate the net effect of urban land-use conversion on SOC pools for the same cities; (iii) use the National Land Cover Database to extrapolate total SOC pools for each of the lower 48 U.S. states; and (iv) compare these totals with aboveground totals of carbon storage by trees. Residential soils in Baltimore had SOC densities that were approximately 20 to 34% less than Moscow or Chicago. By contrast, park soils in Baltimore had more than double the SOC density of Hong Kong. Of the six cities, Atlanta and Chicago had the highest and lowest SOC densities per total area, respectively (7.83 and 5.49 kg m(-2)). On a pervious area basis, the SOC densities increased between 8.32 (Oakland) and 10.82 (Atlanta) kg m(-2). In the northeastern United States, Boston and Syracuse had 1.6-fold less SOC post- than in pre-urban development stage. By contrast, cities located in warmer and/or drier climates had slightly higher SOC pools post- than in pre-urban development stage (4 and 6% for Oakland and Chicago, respectively). For the state analysis, aboveground estimates of C density varied from a low of 0.3 (WY) to a high of 5.1 (GA) kg m(-2), while belowground estimates varied from 4.6 (NV) to 12.7 (NH) kg m(-2). The ratio of aboveground to belowground estimates of C storage varied widely with an overall ratio of 2.8. Our results suggest that urban soils have the potential to sequester large amounts of SOC, especially in residential areas where management inputs and the lack of annual soil disturbances create conditions for net increases in SOC. In addition, our analysis suggests the importance of regional variations of land-use and land-cover distributions, especially wetlands, in estimating urban SOC pools.     

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.     

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.