Dissipation of polycyclic aromatic hydrocarbons (PAHs) in the rhizosphere: Synthesis through meta-analysis

Polycyclic aromatic hydrocarbons (PAHs) are widespread and persistent organic pollutants with high carcinogenic effect and toxicity; their behavior and fate in the soil-plant system have been widely investigated. In the present paper, meta-analysis was used to explore the interaction between plant growth and dissipation of PAHs in soil based on the large body of published literature. Plants have a promoting effect on PAH dissipation in soils. There was no difference in PAH dissipation between soils contaminated with single and mixed PAHs. However, plants had a more obvious effect on PAH dissipation in freshly-spiked soils than in long-term field-polluted soils. Additionally, a positive effect of the number of microbial populations capable of degrading PAHs was observed in the rhizosphere compared with the bulk soil. Our meta-analysis established the importance of the rhizosphere effect on PAH dissipation in variety of the soil-plant systems.     

A comparative study on the uptake of polycyclic aromatic hydrocarbons by Anodonta californiensis

Uptake of polycyclic aromatic hydrocarbons (PAHs) by the freshwater bivalve mollusc Anodonta californiensis was examined in the presence and absence of surfactant in order to gain further insight into mixture toxicity and to predict whether certain mixtures have negative and/or positive effects on aquatic organisms. In the presence of surfactant, the uptake of anthracene or chrysene was higher than that of naphthalene, given the same concentration in the solution. In the absence of surfactant, the trend was similar, but the uptakes were increased by approximately 100% compared to those in the presence of surfactant. On the uptake of naphthalene, the presence of anthracene showed only minor influence. The uptake of anthracene was affected by both naphthalene and chrysene. The uptake of chrysene was influenced by neither naphthalene nor anthracene. There was no observable displacement of divalent cations from the surface of the gill membrane by any of the PAHs studied.     

A directional passive air sampler for monitoring polycyclic aromatic hydrocarbons (PAHs) in air mass

A passive air sampler was developed for collecting polycyclic aromatic hydrocarbons (PAHs) in air mass from various directions. The airflow velocity within the sampler was assessed for its responses to ambient wind speed and direction. The sampler was examined for trapped particles, evaluated quantitatively for influence of airflow velocity and temperature on PAH uptake, examined for PAH uptake kinetics, calibrated against active sampling, and finally tested in the field. The airflow volume passing the sampler was linearly proportional to ambient wind speed and sensitive to wind direction. The uptake rate for an individual PAH was a function of airflow velocity, temperature and the octanol-air partitioning coefficient of the PAH. For all PAHs with more than two rings, the passive sampler operated in a linear uptake phase for three weeks. Different PAH concentrations were obtained in air masses from different directions in the field test.     

Variations in concentrations and compositions of polycyclic aromatic hydrocarbons (PAHs) in coals related to the coal rank and origin

The release of unburnt coal particles and associated polycyclic aromatic hydrocarbons (PAHs) may cause adverse impacts on the environment. This study assessed variations in the concentration and composition of PAHs in a set of fifty coal samples from eleven coal basins worldwide. The maximum PAH concentrations at high volatile bituminous rank were recorded in samples from a single basin. Considering the entire sample set, the highest PAH concentrations were in fact found outside of this rank range, suggesting that the maceral composition and thus the coal’s origin also influenced PAH concentrations. The examination of the PAH compositions revealed that alkylated 2-3 ring PAHs remain dominant compounds irrespective of coal rank or origin. Multivariate analysis based on PAH and maceral content, bulk and maturity parameters allowed the recognition of seven groups with different rank and origin within the coal sample set.     

Removal of polycyclic aromatic hydrocarbons from aged-contaminated soil using cyclodextrins: experimental study

The removal of polycyclic aromatic hydrocarbons (PAHs) from soil using water as flushing agent is relatively ineffective due to their low aqueous solubility. However, addition of cyclodextrin (CD) in washing solutions has been shown to increase the removal efficiency several times. Herein are investigated the effectiveness of cyclodextrin to remove PAH occurring in industrially aged-contaminated soil. Beta-cyclodextrin (BCD), hydroxypropyl-beta-cyclodextrin (HPCD) and methyl-beta-cyclodextrin (MCD) solutions were used for soil flushing in column test to evaluate some influent parameters that can significantly increase the removal efficiency. The process parameters chosen were CD concentration, ratio of washing solution volume to soil weight, and temperature of washing solution. These parameters were found to have a significant and almost linear effect on PAH removal from the contaminated soil, except the temperature where no significant enhancement in PAH extraction was observed for temperature range from 5 to 35 degrees C. The PAHs extraction enhancement factor compared to water was about 200.     

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.     

The behaviors and fate of polycyclic aromatic hydrocarbons (PAHs) in a coking wastewater treatment plant

The occurrence, behaviors and fate of 18 PAHs were investigated in a coking wastewater treatment plant in Songshan coking plant, located in Shaoguan, Guangdong Province of China. It was found that the target compounds occurred widely in raw coking wastewater, treated effluent, sludge and gas samples. In raw coking wastewater, high molecular weight (MW) PAHs were the dominant compounds, while 3-6 ring PAHs predominated in the final effluent. The dominant compounds in gas samples were phenathrene, fluoranthene and pyrene, while they were fluoranthene, pyrene, chrysene and benzo[k]fluoranthene for sludge. The process achieved over 97% removal for all the PAHs, 47-92% of eliminations of these target compounds in liquid phase were achieved in biological stage. Different behaviors of PAHs were observed in the primary tank, anaerobic tank, aerobic tank, hydrolytic tank and coagulation tank units, while heavier and lower ones were mainly removed in anaerobic tank and aerobic tanks, respectively. Regarding the fate of PAHs, calculated fractions of mass losses for low MW PAHs due to transformation and adsorption to sludge accounted for 15-50% and 24-49%, respectively, while the rest was less than 1%. For high MW PAHs, the mass losses were mainly due to adsorption to sludge and separation with tar (contributing 56-76% and 22-39%, respectively), and the removal through transformation was less.     

Seasonal variation of polycyclic aromatic hydrocarbons (PAHs) emissions in China

A regression model based on the provincial energy consumption data was developed to calculate the monthly proportions of residential energy consumption compared to the total year volume. This model was also validated by comparing with some survey and statistical data. With this model, a PAHs emission inventory with seasonal variation was developed. The seasonal variations of different sources in different regions of China and the spatial distribution of the major sources in different seasons were also achieved. The PAHs emissions were larger in the winter than in the summer, with a difference of about 1.3-folds between the months with the largest and the smallest emissions. Residential solid fuel combustion dominated the pattern of seasonal variation with the winter-time emissions as much as 1.6 times as that in the summer, while the emissions from wild fires and open fire straw burning was mainly concentrated during the spring and summer.     

Lead and polycyclic aromatic hydrocarbons (PAHs) in surface soil from day care centres in the city of Bergen, Norway

Surface soil (0-2cm) quality in 87 day care centres in the city of Bergen, Norway has been studied. Approximately 45% of the day care centres contained Pb and PAH values above recommended action levels. There are clear variations between different areas of the city. The old central part of the city hosts most of the contaminated day care centres. In suburban areas most of the day care centres have Pb and PAH concentrations below action levels. City fires, gas work emission, lead-based paint, and traffic are probably important anthropogenic contamination sources, together with uncontrolled transportation of soil from contaminated to clean areas. Geological or other natural sources are probably not an important contributor to the high levels of lead and PAH.     

Characterization of extractable and non-extractable polycyclic aromatic hydrocarbons in soils and sediments from the Pearl River Delta, China

Formation of bound residues of pollutants in soils and sediments is an important process to control the fate of pollutants in the environment. The most of bound residue is not solvent extractable. In this paper, we measured both extractable and non-extractable polycyclic aromatic hydrocarbons (PAHs) in different organic matter fractions of samples from the Pearl River Delta, China. Non-extractable PAHs concentration was 234.45-1424.57 μg/kg and accounted for 33.78-57.44% of total PAHs. 2-3 Ring PAHs were the dominant species and differed in concentration substantially between the samples. The atomic ratio of PAHs over organic-C in the fractions ordered as solvent soluble organic matter > humin > humic acids, matching the content of aliphatic moieties in the fractions of organic matter. The ratio of extractable and non-extractable PAHs may relate to the aging process of PAHs in soil and sediment.     

Black carbon (BC) in urban and surrounding rural soils of Beijing, China: spatial distribution and relationship with polycyclic aromatic hydrocarbons (PAHs)

The concentrations of black carbon (BC), total organic carbon (TOC) and polycyclic aromatic hydrocarbons (PAHs) have been determined in soils from urban and rural areas of Beijing. The rural area can be divided into plain and mountainous areas which are close to and relatively far from the urban area, respectively. Concentration of BC (5.83 ± 3.05 mg g⁻¹) and BC/TOC concentration ratio (0.37 ± 0.15) in Beijing’s urban soil are high compared with that in world background soils and rural soils of Beijing, suggesting the urban environment to be an essential source and sink of BC. Concentration of BC in the urban area decreases from the inner city to exterior areas, which correlates with the urbanization history of Beijing and infers accumulation of BC in old urban soils. Black carbon in Beijing soils mainly comes from fossil fuel combustion, especially traffic emission. Median PAH concentration in the urban area (502 ng g⁻¹) is one order of magnitude higher than that in the rural plain (148 ng g⁻¹) and mountainous area (146 ng g⁻¹) where PAHs are supposed to mainly come from atmospheric deposition from the urban area. Concentrations of BC correlate significantly with those of PAHs (p < 0.01, except naphthalene) in the urban area and with those of heavier 4-, 5- and 6- ring PAHs (p < 0.01) in the adjacent rural plain area, while there is no significant correlation with any PAH in the farther rural mountainous area.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Size distribution of polycyclic aromatic hydrocarbons in a roadway tunnel in Lisbon, Portugal

Atmospheric aerosols of four aerodynamic size ranges were collected using high volume cascade impactors in an extremely busy roadway tunnel in Lisbon (Portugal). Dust deposited on the tunnel walls and guardrails was also collected. Average particle mass concentrations in the tunnel atmosphere were more than 30 times higher than in the outside urban background air, revealing its origins almost exclusively from fresh vehicle emissions. Most of the aerosol mass was concentrated in submicrometer fractions (65%), and polycyclic aromatic hydrocarbons (PAH) were even more concentrated in the finer particles with an average of 84% of total PAH present in sizes smaller than 0.49 μm. The most abundant PAH were methylated phenanthrenes, fluoranthene and pyrene. About 46% of the total PAH mass was attributed to lower molecular weight compounds (two and three rings), suggesting a strong influence of diesel vehicle emissions on the production of local particulate PAH. The application of diagnostic ratios confirmed the relevance of this source of PAH in the tunnel ambient air. Deposited dust presented PAH profiles similar to the coarser aerosol size range, in agreement with the predominant origin of coarser aerosol particles from soil dust resuspension and vehicle wear products.     

Estimation of the annual scavenged amount of polycyclic aromatic hydrocarbons by forests in the Pearl River Delta of Southern China

Leaves of six main tree species from the Pearl River Delta (PRD) in Southern China were collected to identify the interspecific variability, the spatial variability and the seasonal variations of polycyclic aromatic hydrocarbons' (PAHs) concentrations, and to calculate the amount of PAHs removed by leaves. PAHs concentrations in pine needles were much higher than in broad-leaves and leaves from urban/industrial areas (Baiyunshan and Heshan) exhibited two times greater concentrations than leaves from the rural area (Dinghushan). Seasonal variations of PAHs in leaves occurred with lesser concentrations in September. Leaves in PRD scavenged 3.7 ± 0.9 t PAHs y⁻¹, accounting for about 10% of the total amount emitted in this region. This result suggests that forests play an important role in the fate of PAHs.     

Long-term atmospheric bulk deposition of polycyclic aromatic hydrocarbons (PAHs) in rural areas of Southern Germany

A novel passive sampling technique using a funnel–adsorber–cartridge device was adopted and validated in the field during a long-term monitoring program on the atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in three rural regions of southern Germany. Apart from seasonal variations, fairly stable annual deposition rates around 200 μg m⁻² yr⁻¹ for the sum of PAHs were obtained. The time-integrating passive samplers showed that spatial variability due to topography was negligible and differences between open-field and forest deposition were within a factor of 2. Based on correlations with ambient temperature, advection was identified as the most important factor that controls the atmospheric deposition of PAHs. Gas-adsorption contributes significantly to the deposition of the semivolatile compounds in forests, but particle deposition seems to be the major pathway for all PAHs.     

Determination of polycyclic aromatic hydrocarbons in urban street dust: implications for human health

The determination of sixteen polycyclic aromatic hydrocarbons in urban street dust has been done. Samples were collected from 12 sampling locations in a city centre location (Newcastle upon Tyne, north east England) and extracted using in situ pressurised fluid extraction followed by gas chromatography mass spectrometry. From the results it was possible to identify three groups, with respect to PAH concentration, with PAH contents ranging between 0.6-2.3 mg kg⁻¹, 15.6-22.5 mg kg⁻¹ and 36.1-46.0 mg kg⁻¹. The total PAH content of samples from these sampling sites has been compared to 22 urban locations around the world; comparable levels were found in these samples compared to the other cities around the world.The potential source of PAHs has been investigated by investigating the proportion of pyrogenic and petrogenic material in urban street dust using specific individual PAH ratios. The results indicate that the PAH content of urban street dust from the chosen sites are more likely to be due to pyrogenic sources i.e. vehicle exhaust emissions. The particle size fractions (<63 μm; 63-125 μm; 125-250 μm; 250-500 μm; 500-1000 μm; and 1000-2000 μm) of individual PAHs in three selected sampling sites was investigated. In two of the selected sites the PAH content was independent of particle size whereas in sampling site 10 elevated PAH levels are noted in the <63 μm size fraction. Sampling site 10 is located at the junction of three road tributaries which are used as major access points to the east of the city centre. Finally, the potential health risk for unintentional consumption of PAHs was assessed in terms of a mean daily intake (based on an ingestion rate of 100 mg d⁻¹). It was found that all 4-6 membered ring PAHs had concentrations in excess of the mean daily intake thereby reflecting a potential health risk, particularly in the smallest size particle fractions.     

固相萃取-气相色谱/质谱法测定水中多环芳烃

建立了固相萃取-气相色谱／质谱联用测定水中多环芳烃(PAHs)的分析方法．优化了固相萃取条件。结果表明,固相萃取效率高、萃取时间短,采用MS的选择离子检测方式对实际水样中PAHs进行定性定量分析,平均回收率在80．4％～115％之间,相对标准偏差为7．03％～18．5％,方法的检出限在0．010～0．020μg／L之间。通过实际样品中PAHs的分析表明,该法快速,溶剂用量少,能满足痕量分析的要求。     

Sources and distribution of polycyclic aromatic hydrocarbons in sediments from the Spanish northern continental shelf. Assessment of spatial and temporal trends

The distribution of polycyclic aromatic hydrocarbons was determined in surface sediments collected at 36 stations along the Spanish Northern continental shelf in March and September 2003, and February 2005. Concentrations of PAHs (Σ13 parent components) were in the range of 22-47528 μg/kg dw, the highest values corresponding to coastal urban-industrial hotspots and decreasing offshore. Sediment quality guidelines (SQGs) showed that concentrations of total PAHs were below the threshold effect level (TEC) in 27 stations (81%) and above in 7, two of which (Gijon and Bilbao) were above the probable effect concentration (PEC). The detailed study of diagnostic ratios suggested a rather uniform mixture of petrogenic and pyrolytic PAH sources along the continental shelf, with a slight decrease of the latter moving westwards and offshore. In order to assess the incidence of sediment sampling on the variability of the results, selected stations were also monitored in February and September 2004 and September 2005. The average field variance of the values obtained for each station was 31% that decreased to 23% when the values were normalized to TOC.     

Effects of fulvic acid concentration and origin on photodegradation of polycyclic aromatic hydrocarbons in aqueous solution: Importance of active oxygen

With an Xe arc lamp house as simulated sunlight, the influences of fulvic acid (FA) concentration and origins on photodegradation of acenaphthene, fluorine, phenanthrene, fluoranthene and pyrene in aqueous solution have been studied. Similar effects of FAs, collected from five places around China, on polycyclic aromatic hydrocarbon (PAH) photodegradation have been observed. Active oxygen was of significance in PAH photodegradation with the presence of FAs. For systems with 1.25 mg L⁻¹ FAs, the contributions of OH to PAH photodegradation rates were from 33% to 69%. FAs had two opposite effects, i.e., stimulating the generation of active oxygen and advancing PAH photodegradation; competing with PAHs for energy and photons and restraining PAH photodegradation. Generally, photodegradation rates of the 5 PAHs decreased with the increase of FAs concentration; except fluoranthene and pyrene were advanced in solutions with low FA concentration. The influences of FA concentration on PAH photodegradation were more significant than FA origin.     

Evaluation of the STP model: comparison of modelled and experimental results for ten polycyclic aromatic hydrocarbons (PAHs)

Screening level risk assessment models are used by many countries to assess the treatability of organic chemicals during the sewage treatment process, especially those that are new to commerce. The performance of one such model, the sewage treatment plant model, is evaluated in the current study by comparing model predictions with actual measurement data collected at various stages of a typical full-scale activated sludge type sewage treatment plant. A suite of ten polycyclic aromatic hydrocarbons (PAHs) with widely varying physico–chemical properties were monitored for the comparison. Model predicted removal efficiencies were in very good agreement with those measured for all ten PAHs. Observed chemical concentrations and their trends at various stages of the sewage treatment process were also well simulated by the model. Results also suggest that a reasonable first approximation estimate of a range for the biodegradation half-life needed for the model may be obtained by dividing reported aqueous biodegradation half-life by scaling factors of 50 and 150.