Degradation of selected polycyclic aromatic hydrocarbons in coastal sediments: Importance of microbes and polychaete worms

Rates of degradation of polycyclic aromatic hydrocarbons (PAH) were examined after addition of crude oil enriched with anthracene, fluoranthene, benz(a)anthracene, and benzo(a)pyrene to coastal sediments in a laboratory (20°) flowing seawater system. Three types of sediment (fine sand, medium sand, and marsh sediment) with and without the benthic polychaete worm, Capitella capitata, were used. After extraction from the sediment, PAH concentrations were measured by liquid chromatography with fluorescent detection. Microbial degradation was studied by incubating sediments with radioactive PAH and measuring subsequent production of ¹⁴C0₂. Concentrations of the four PAH decreased significantly with time in fine and medium sized sands. PAH levels also decreased in marsh sediment but trends were not significant (P < 0.05). C. capitata stimulated PAH degradation. Microbial degradation was more rapid in upper surfaces than in lower layers of the sediments.     

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

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

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

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

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

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

真菌漆酶氧化蒽的影响因子及其产物毒性研究

The transformation profiles of polycyclic aromatic hydrocarbons （PAHs） by pure laccases from Trametes versicolor and Pycnoporus sanguineus, and the optimal reaction conditions （acetonitrile concentration, pH, temperature and incubation time） were determined. Anthracene was the most transformable PAH by both laccases, followed by benzo[a]pyrene, and benzo[a]anthracene. Laccase-mediator system （LMS） could not only improve the PAH oxidation but also extend the substrate types compared to laccase alone. 5e/0 or 10~ （v/v） of acetonitrile concentration, pH 4, temperature of 40 ~C, and incubation time of 24 h were most favorable for anthracene oxidation by laccase from T. versicolor or P. sanguineus. The gas chromatography-mass spectrometry analysis indicated that 9,10- anthraquinone was the main product of anthracene transformed by laccase from T. versicolor. Microtox test results showed that both anthracene and its laccase-transformation products were not acute toxic compounds, suggesting that laccase-treatment of anthracene would not increase the acute toxicity of contaminated site.     

Influence of organic amendments used for benz[a]anthracene remediation in a farmland soil: pollutant distribution and bacterial changes

Purpose

Organic amendments are usually carried out at field-scale for efficient remediation of organic pollutants; however, their effects on pollutant distribution and the corresponding microbial mechanisms were rarely discussed. The main aim of this study was to compare the fate of benz[a]anthracene in soil amended by several bioremediation materials and underlying microbial mechanisms.

Materials and methods

In this study, the potential for biotransformation of polycyclic aromatic hydrocarbon in a farmland soil was investigated in microcosms spiked with ¹⁴C-benz[a]anthracene as the tracer. A series of organic amendments including lignin, straw, mushroom culture waste, and cow manure, as well as a fungal inoculum of Pleurotus ostreatus, were compared. Illumina sequencing was introduced to reveal the bacterial community in different amendments. The metagenomic function was predicted with the bioinformatics tool of phylogenetic investigation of communities by reconstruction of unobserved states (PICRUSt).

Results and discussion

From the results, the lignin-contained substrates (lignin, straw, mushroom culture waste) showed increase trend in the dissipation of benz[a]anthracene, while Pleurotus ostreatus and cow manure resulted in opposite trends. Specifically, mushroom culture waste mainly increased ¹⁴C to the formation of humin-bound residue (39.5?±?6.8%); lignin amendment significantly (P?<?0.05) enhanced the mineralization to CO₂ (7.38?±?0.89%) and humic acid–related nonextractable residue (9.77?±?0.45%). The influence of straw on the environmental fate of benz[a]anthracene was marginal. High-throughput sequencing of 16S rRNA genes demonstrated that mushroom culture waste and lignin significantly changed bacterial community composition, leading to increases in the relative abundance of Pseudomonadaceae, Methylophilaceae, Bacillaceae, and Burkholderiaceae. Moreover, the result of PICRUSt showed that the genes-encoding bacterial cytochrome P450 enzymes were significantly increased in the lignin treatment, suggesting a possible co-metabolism between lignin degradation and PAH mineralization.

Conclusions

These findings suggest lignin-containing organic amendments could be promising soil remediation agents of benz[a]anthracene by stimulating mineralization and sequestration of pollutants.

     

Human Health Risk Assessment of 16 Priority Polycyclic Aromatic Hydrocarbons in Soils of Chattanooga, Tennessee, USA

South Chattanooga has been home to foundries, coke furnaces, chemical, wood preserving, tanning, and textile plants for over 100?years. Most of the industries were in place before any significant development of residential property in the area. During the 1950s and 1960s, however, the government purchased inexpensive property and constructed public housing projects in South Chattanooga. Many neighborhoods that surround the Chattanooga Creek were previous dumping grounds for industry. Polycyclic aromatic hydrocarbons (PAHs) comprised the largest component of the dumping and airborne industrial emissions. To address human exposure to these PAHs, a broad study of South Chattanooga soil contaminant concentrations was conducted on 20 sites across the city. Sixteen priority pollutant PAHs were quantified at two depths (0?C10 and 10?C20?cm) and compared against reference site soils, as well as to soils from industrially impacted areas in Germany, China, and the USA. From these data, the probability that people would encounter levels exceeding the United States Environmental Protection Agency (USEPA) residential preliminary remediation goals (PRG) was calculated. Results indicate that South Chattanooga soils have relatively high concentrations of total PAHs, specifically benzo[a]pyrene (B[a]P). These high concentrations of B[a]P were somewhat ubiquitous in South Chattanooga. Indeed, there is a high probability (88?%) of encountering soil in South Chattanooga that exceeds the USEPA PRG for B[a]P. However, there is a low probability (15?%) of encountering a site with ??PAHs exceeding USEPA PRG guidelines.     

Hydrocarbon status of soils under atmospheric pollution from a local industrial source

Contents and compositions of bitumoids, polycyclic aromatic hydrocarbons (PAHs), and free and retained hydrocarbon gases in soils along a transect at different distances from the local industrial source of atmospheric pollution with soot emissions have been studied. The reserves of PAHs progressively decrease when the distance from the source increases. Among the individual PAHs, the most significant decrease is observed for benzo[a]pyrene, tetraphene, pyrene, chrysene, and anthracene. On plowlands, the share of heavy PAHs—benzo[ghi]perylene, benzo[a]pyrene, perylene, etc.—is lower than in the forest soils. In automorphic soils of the park zone adjacent to the industrial zone, the penetration depth of four-, five-, and sixring PAHs from the atmosphere is no more than 25 cm. In soils under natural forest vegetation, heavy PAHs do not penetrate deeper than 5 cm; in tilled soils, their penetration depth coincides with the lower boundary of plow horizons. Analysis of free gases in the soil air revealed hydrocarbons only under forest. From the quantitative and qualitative parameters of the content, reserves, and compositions of different hydrocarbons, the following modification types of hydrocarbon status in the studied soils were revealed: injection, atmosedimentation–injection, atmosedimentation–impact, atmosedimentation–distant, and biogeochemical types.     

Formation of polycyclic aromatic hydrocarbons in northern and middle taiga soils

An integrated study of the qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric precipitation-soil-lysimetric water system was performed using high performance liquid chromatography. It was shown that the accumulation of low-molecular PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, and chrysene) in soils is due to the transformation of organic matter and the regional transport and deposition of PAHs with atmospheric precipitation on the underlying surface. High-molecular polyarenes (benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene) mainly result from the decomposition of soil organic matter.     

The effect of concentrations and properties of phenanthrene, pyrene, and benzo(a)pyrene on desorption in contaminated soil aged for 1 year

Purpose

The choice and timing of microorganisms added to soils for bioremediation is affected by the dominant bioavailable contaminants in the soil. However, changes to the concentration of bioavailable PAHs in soil are not clear, especially when several PAHs coexist. This study investigated the effects of PAH concentration and chemical properties on desorption in meadow brown soil after a 1-year aging period, which could reflect changes of PAH bioavailability during bioremediation.

Materials and methods

Based on the percentage of different molecular weights in a field investigation, high-level contaminated soil (HCS) and low-level contaminated soil (LCS) were prepared by adding phenanthrene (PHE), pyrene (PYR) and benzo(a)pyrene (BaP) to uncontaminated meadow brown soil. The concentrations of HCS and LCS were 250 mg?kg^?1 (PHE, PYR, and BaP: 100, 100, and 50 mg?kg^?1) and 50 mg?kg^?1 (PHE, PYR, and BaP: 20, 20, and 10 mg?kg^?1) respectively. The soils were aged for 1 year, after which desorption was induced by means of a XAD-2 adsorption technique over a 96-h period.

Results and discussion

The range of the rapidly desorbing fraction (F _rap) for PHE, PYR, and BaP in HCS and LCS was from 1.9 to 27.8 %. In HCS, desorption of PYR was most difficult, and the rate constant of very slow desorption (K _vs) of PYR was 8 orders of magnitude lower than that of BaP, which had similar very slow desorbing fractions (49.8 and 50.5 %, respectively). However, in LCS, desorption of PYR was the easiest; the K_vs of PYR was 8–10 orders of magnitude higher than those of PHE and BaP. In HCS, the time scale for release of 50 % of the PAHs was ranked as BaP?>?PYR?>?PHE, while in LCS this was BaP?>?PHE?>?PYR.

Conclusions

The combined effect of PAH concentrations and properties should be taken into account during desorption. The desorption of PAH did not always decrease with increasing molecular weight, and the desorption of four-ring PAHs might be special. These results are useful for screening biodegrading microbes and determining when they should be added to soils based on the dominant contaminants present during different periods, thus improving the efficiency of soil bioremediation.     

Long-Range Atmospheric Transport and Local Pollution Sources on PAH Concentrations in a South European Urban Area. Fulfilling of the European Directive

A 12 months study on urban atmospheric concentrations of polycyclic aromatic hydrocarbons (PAH) contained in the particulate matter with an aerodynamic diameter less than or equal to 10 microns (PM10) was carried out in Zaragoza (Spain) from July 12th, 2001 to July 26th, 2002 by using a high-volume air sampler able to collect the PAH supported on a Teflon-coated fibre glass filter. Samples were analysed by using Gas Chromatography Mass Spectrometry (GC-MS/MS). PAH of high molecular weight, indeno[1,2,3-cd]pyrene (IcdP), benzo[g,h,i]perylene (BghiP) and coronene (Co) were the most abundant compounds. The concentrations of benz[a]pyrene equivalent carcinogenic power (BaP-eq) showed a mean value of 0.7 ng/m³ with 22.5% of the samples exceeding the 1.0 ng/m³ guide value established by the European Directive. These episodes were mainly produced during cold season. Regarding meteorological variables, a positive effect of the prevalent wind “cierzo” (NW direction) over the Zaragoza city was confirmed from the environmental point of view. The NE, E and S directions, corresponding to highway and industrial areas were the directions showing the high PAH atmospheric concentrations. Despite the proximity of a high-level traffic highway, stationary sources related to industry were the dominant source of PAH in the sampled area. Vehicular emissions and natural gas home heating also contributed to PAH concentrations. The predominance of local pollution sources versus long-range transport on PAH concentrations was shown. However, the contribution of long-range transport of anthropogenic origin from other European areas was reflected for specific dates on PAH concentrations and PM10 levels.     

Studying the Effects of Two Various Methods of Composting on the Degradation Levels of Polycyclic Aromatic Hydrocarbons (PAHs) in Sewage Sludge

The research comprised of studying the effect composting sewage sludge with sawdust and vermicomposting with earthworm Eisenia fetida has on the degradation of 16 polycyclic aromatic hydrocarbons (PAHs). Raw rural sewage sludge prior composting was more contaminated with PAHs than urban sewage sludge, in both cases exceeding EU cutoff limits of 6 mg/kg established for land application. Dibenzo[a,h]anthracene (DBahAnt), acenaphtylene (Acy) and indeno[1,2,3-c,d]pyrene (IPyr) were predominant in rural sewage sludge, whilst the urban sewage sludge contained the highest concentrations of benzo[b]fluoranthene (BbFl), benzo[k]fluoranthene (BkFl) and indeno[1,2,3-c,d]pyrene (IPyr). Thirty days of composting with sawdust has caused a significant reduction of 16 PAHs on average from 26.07 to 4.01 mg/kg (84.6%). During vermicomposting, total PAH concentration decreased on average from 15.5 to 2.37 mg/kg (84.7%). Vermicomposting caused full degradation of hydrocarbons containing 2 and 6 rings and significant reduction of PAHs with 3 aromatic rings (94.4%) as well as with 5 aromatic rings (83.2%). The lowest rate of degradation (64.4%) was observed for hydrocarbons with 4 aromatic rings such as fluoranthene, benzo(a)anthracene, chrysene and pyrene. On the other hand, the highest level of degradation was determined for PAHs with 2 rings (100%), 3 rings (88%) and 6 aromatic rings in the molecule (86.9%) after composting with sawdust. Acenaphthene and pyrene were found to be the most resistant to biodegradation during both composting methods.     

Rapid, semimicro method for determination of polycyclic aromatic hydrocarbons in shellfish by automated gel permeation/liquid chromatography

A simple, rapid, easily automated method is described for the determination of polycyclic aromatic hydrocarbons (PAHs) in shellfish such as American lobster (Homarus americanus) and blue mussel (Mytilus edulis). PAHs are extracted from small amounts (1-8 g) of tissue by saponification in 1N ethanolic potassium hydroxide followed by partitioning into 2,2,4-trimethylpentane. This solution is evaporated just to dryness by rotary evaporation and the residue is dissolved in cyclohexane-dichloromethane (1 + 1) for gel permeation chromatography (GPC) on Bio-Beads SX-3. The GPC procedure is ideal as a screening method in the range 25-18 000 ng PAHs/g tissue. If individual PAH measurements are required, the appropriate GPC fraction is collected and PAHs are separated by reverse phase liquid chromatography (LC) with fluorometric detection. Individual PAHs at concentrations as low as 0.25-10 ng/g can be determined. Recoveries of added fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene were quantitative, with relative standard deviations ranging from 0.0 to 16.9%.     

Effect of Anthracene and Pyrene on Dehydrogenases Activity in Soils Exposed and Unexposed to PAHs

The effect of anthracene and pyrene on dehydrogenases activitywas compared between freshly spiked soils and soils previouslyexposed to PAHs. Four different soils (two soils from anunpolluted rural area and two soils from highly pollutedindustrial areas) were spiked with anthracene and pyrene atthe levels of 1, 10, 100 and 400 mg Σ2PAH per kg of soil (laboratory experiments). The soil samples were moisted to60% of water holding capacity and incubated in the dark at 18-20 °C. Dehydrogenase activity was determined after 7 and30 days. The results indicate that long-term exposure of soilfrom an industrial area to high level of PAHs (Σ13PAH = 40 mg kg^-1) caused the acclimatisation of soilmicroorganisms and lowered their sensitivity to these compounds.After the longer incubation period (30 days vs. 7 days)the soil microorganisms in the uncontaminated rural samples showed an increase in their tolerance to the freshly introduced PAH compounds; in the industrial soils the effect was less pronounced. However, this apparent adaptation of soil microorganisms may be also partly explained by the dissipation and/or ageing processes of anthracene and pyrene during incubation.     

Polycyclic aromatic hydrocarbons in marine organisms from the Gulf of Naples, Tyrrhenian Sea

Polycyclic aromatic hydrocarbons (PAHs) were determined by an HPLC method with fluorescence detection in bivalves (Mitylus galloprovincialis), cephalopods (Todarodes sagittatus), crustaceans (Aristeus antennatus), and fish (Mullus surmeletus, Scomber scombrus, Micromesistius poutassou, and Merluccius merluccius) caught in the Gulf of Naples (Tyrrhenian Sea, Italy). Anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene, benzo(b)fluoranthene, and benzo(k)fluoranthene were detected, at different concentrations, in all of the examined marine organisms, whereas benzo(a)pyrene, dibenz(a,h)anthracene, benzo(g,h,i)perylene, and indeno(1,2,3-cd)pyrene were found only in Mediterranean mussels. Of mussels collected in winter 71.43% exceeded the maximum residual levels (MRL) fixed for the benzo(a)pyrene in European Regulation 208/2005/EC, whereas all samples collected in summer reported values lower than this limit. In comparison to the other marine organisms, the mussels showed the highest PAH concentrations (p < 0.01). Fish showed total PAH levels lower than those of cephalopods and, in particular, European hake showed the lowest values (6.06 ng/g of fresh weight).     

New alternative method of benzo[a]pyrene extractionfrom soils and its approbation in soil under technogenic pressure

Purpose

The optimization of benzo[a]pyrene extraction conditions by subcritical water extraction method from soils is the purpose of the research. The optimal conditions for benzo[a]pyrene recovery are 30-min extraction by water in a special steel cartridge at 250 °C and 100 atm.

Materials and methods

Studies were conducted on the soils of monitoring plots subjected to Novocherkassk Power Station emissions. Monitoring plots were established at different distances from the Novocherkassk Power Station (NPS; 1.0–20.0 km).

Results and discussion

It was shown that the use of water in subcritical state as a solvent for benzo[a]pyrene extraction from soil allows to avoid large volumes of organic solvents and to decrease the time of sample preparation. It is shown that the maximum benzo[a]pyrene maintenance was observed in soils of the monitoring plots located most close (to 5 km) to a pollution source in the area of the prevailing direction of a wind rose. Dynamics of pollutant accumulation in soils depend on number of Novocherkassk state district power station emissions.

Conclusions

The method of benzo[a]pyrene subcritical water extraction from soil was developed and approbated during long-term monitoring researches of technogenic polluted territories. The optimum conditions for benzo[a]pyrene extraction from soil have been determined: the soil is treating by subcritical water at 250 °C and 100 atm of pressure for 30 min. Trends in the accumulation of benzo[a]pyrene in soil zones of the thermal power plant influence have been researched over a 5-year period of monitoring observations by subcritical water extraction method. Benzo[a]pyrene accumulation in soils depends on the technogenic emissions to the atmosphere from Novocherkassk power station and on the soil physical and chemical properties.

     

Gehalte an Polycyclischen Aromatischen Kohlenwasserstoffen (PAK) und deren Verteilungsmuster in unterschiedlich belasteten Böden

Contents of polycyclic aromatic hydrocarbons (PAH) and their distribution pattern in soils with different contamination levels In order to study the PAH-contamination of soils in North Rhine Westfalia, soil samples were taken at different sites and analysed for six PAH. The sites were selected with regard to different forms of land use such as arable land and pastures in rural areas and gardens in urban areas and with regard to varying immission situations. The results are valued according to reference (RW) and test values (PW) of the Netherlands Guidelines for soil restoration. The reference values of these guidelines characterizing normal contents are regularly and in part distinctly exceeded for fluoranthene and benzo(a)pyrene at some sites (coking plant, alluvial meadow soils, allotment gardens, close to a highway). The check values which imply more exact investigations are only exceeded at the most contaminated site, a coking plant. The PAH patterns at the different sites investigated depend on the number and kind of PAH sources. PAH typical for motor vehicle emission (benzo(b)fluoranthene, benzo(g,h,i)perylene) are dominating in soils close to a highway, whereas at the cokery site fluoranthene can be found in higher concentrations than the other PAH. In alluvial river soils and in soils of allotment gardens the pattern is more uniform because of diffuse sources with decreasing contents in the order fluoranthene > benzo(a)anthracene > benzo(b) fluoranthene > benzo(g,h,i)perylene > benzo(a)pyrene > benzo(k)fluoranthene. As a guide substance for a first risk assessment benzo(a)pyrene is suitable, since its content shows a strong correlation to the sum of five other PAH. In order to characterize the background contamination of soils with PAH new reference values are proposed.     

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

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

Using in situ solid phase microextraction (SPME) for depth profiling in sediments treated with activated carbon

Purpose

Sediment contamination in US waterways is an expensive and complicated issue, and as acceptance of nontraditional sediment remediation strategies broadens, novel and efficient methods to assess and monitor the bioavailability of hydrophobic organic contaminants (HOCs) in contaminated sediments will play an important role.

Materials and methods

In this project, solid phase microextraction (SPME) fibers inside perforated steel tubes were used as in situ passive samplers to measure polycyclic aromatic hydrocarbon (PAH) concentrations in sediment before and after treatment with activated carbon (AC). Two modes of waterjet amendment injection were used to apply the AC. In the first treatment, a single 2-min injection was shot into the center of a test vessel, and in the second treatment, multiple 7-s injections in a grid were placed in sediment.

Results and discussion

In the single injection, no treatment was observed 5 cm away from the injection, while at 2.5 cm, >90 % decrease of PAH pore water concentration was observed, indicating a similar bioavailability decrease. In the multiple injection experiment, >90 % PAH pore water level reductions were observed throughout the test vessel. Highly contaminated and less contaminated sediments were mixed with 0–5 % AC by weight to develop AC treatment curves. Over 99 % reduction in PAH pore water concentrations and bioavailability was observed in the less contaminated sediment at 3 % AC, while 99 % reduction was never reached even at 5 % AC addition in the highly contaminated sediment. Different treatment curves were observed for the different contaminated sediments. In situ equilibration times were 120, 215, and 250 h for phenanthrene, pyrene, and benzo(a)anthracene, respectively.

Conclusions

The results show that in situ SPME is a viable method to observe AC treatment and evaluate reductions in pore water concentrations and bioavailability.     

Chemometric Study of the Ex Situ Underground Coal Gasification Wastewater Experimental Data

The main goal of the study was the analysis of the parameters of wastewater generated during the ex situ underground coal gasification (UCG) experiments on lignite from Belchatow, and hard coal from Ziemowit and Bobrek coal mines, simulated in the ex situ reactor. The UCG wastewater may pose a potential threat to the groundwater since it contains high concentrations of inorganic (i.e., ammonia nitrogen, nitrites, chlorides, free and bound cyanides, sulfates and trace elements: As, B, Cr, Zn, Al, Cd, Co, Mn, Cu, Mo, Ni, Pb, Hg, Se, Ti, Fe) and organic (i.e., phenolics, benzene and their alkyl derivatives, and polycyclic aromatic hydrocarbons) contaminants. The principal component analysis and hierarchical clustering analysis enabled to effectively explore the similarities and dissimilarities between the samples generated in lignite and hard coal oxygen gasification process in terms of the amounts and concentrations of particular components. The total amount of wastewater produced in lignite gasification process was higher than the amount generated in hard coal gasification experiments. The lignite gasification wastewater was also characterized by the highest contents of acenaphthene, phenanthrene, anthracene, fluoranthene, and pyrene, whereas hard coal gasification wastewater was characterized by relatively higher concentrations of nitrites, As, Cr, Cu, benzene, toluene, xylene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene.