Biosurfactant- and biodegradation-enhanced partitioning of polycyclic aromatic hydrocarbons from nonaqueous-phase liquids

A study was conducted on the effect of two different biological factors, microbial surfactants and biodegradation, on the kinetics of partitioning of polycyclic aromatic hydrocarbons (PAHs) from nonaqueous-phase liquids (NAPLs). The effect of rhamnolipid biosurfactants on partitioning into the aqueous phase of naphthalene, fluorene, phenanthrene, and pyrene, initially dissolved in di-2-ethylhexyl phthalate (DEHP) or 2,2,4,4,6,8,8-heptamethylnonane (HMN), was determined in multiple-solute experiments. Biosurfactants at a concentration above the CMC enhanced the partitioning rate of fluorene, phenanthrene, and pyrene but were ineffective with naphthalene. Enhancement of partitioning was also observed in the presence of suspended humic acid-clay complexes, which simulated the solids often present in the subsurface. Biosurfactants sorbed to the complexes modified PAH partitioning between the NAPL and these solids, increasing the fraction of solid-phase PAH. Biodegradation-driven partitioning was estimated in mineralization experiments with phenanthrene initially present in HMN and three representative soil bacterial strains, differing in their potential adherence to the NAPL. In the three cases, the rates of mineralization were very similar and significantly higher than the abiotic rate of partitioning. Our study suggests that in NAPL-polluted sites, partitioning of PAH may be efficiently enhanced by in situ treatments involving the use of biosurfactants and biodegradation.     

Effect of interface fertilization on biodegradation of polycyclic aromatic hydrocarbons present in nonaqueous-phase liquids

The main goal of this study was to use an oleophilic biostimulant (S-200) to target possible nutritional limitations for biodegradation of polycyclic aromatic hydrocarbons (PAHs) at the interface between nonaqueous-phase liquids (NAPLs) and the water phase. Biodegradation of PAHs present in fuel-containing NAPLs was slow and followed zero-order kinetics, indicating bioavailability restrictions. The biostimulant enhanced the biodegradation, producing logistic (S-shaped) kinetics and 10-fold increases in the rate of mineralization of phenanthrene, fluoranthene, and pyrene. Chemical analysis of residual fuel oil also evidenced an enhanced biodegradation of the alkyl-PAHs and n-alkanes. The enhancement was not the result of an increase in the rate of partitioning of PAHs into the aqueous phase, nor was it caused by the compensation of any nutritional deficiency in the medium. We suggest that biodegradation of PAH by bacteria attached to NAPLs can be limited by nutrient availability due to the simultaneous consumption of NAPL components, but this limitation can be overcome by interface fertilization.     

Micellar solubilization of naphthalene and phenanthrene from nonaqueous-phase liquids

The equilibrium partitioning of the polycyclic aromatic hydrocarbon (PAH) compounds naphthalene and phenanthrene, from nonaqueous-phase liquids (NAPLs) into micellar solutions of five different nonionic polyethoxylated surfactants, is evaluated in this study. A series of synthesized NAPLs, comprised of naphthalene and/or phenanthrene dissolved in hexadecane at varying concentrations, were equilibrated with surfactant solutions in well-mixed batch systems. It was observed that the extent of micellar partitioning of PAH compounds increases linearly with their relative abundance in the NAPLs. A theoretical liquid-liquid partitioning framework that describes PAH equilibrium partitioning between the NAPL, aqueous, and the liquid-like micellar phases is presented. Although the maximum solubilization capacity of micelles is generally higher for naphthalene as compared to phenanthrene, results indicate that with certain NAPLs phenanthrene may be solubilized to a similar extent as naphthalene, even when equal mole fractions of the compounds are present in the NAPLs. Selective solubilization of naphthalene over phenanthrene into micellar solutions of Brij 35 was observed in systems where naphthalene and phenanthrene were both present. The extent of micellar partitioning of phenanthrene was decreased by approximately 18% in the presence of naphthalene, while naphthalene partitioning was unaffected by the presence of phenanthrene.     

Rate-limited solubilization of multicomponent nonaqueous-phase liquids by flushing with cosolvents and surfactants: modeling data from laboratory and field experiments

The impact of rate-limited mass transfer on in-situ cosolvent and single-phase microemulsion flushing for the solubilization of multicomponent nonaqueous-phase liquids (NAPLs) was investigated. Laboratory and field data from both cosolvent and microemulsion flushing studies were modeled using a one-dimensional flow, enhanced-dissolution code. Transport of the flushing agents was described with a one-dimensional advection-dispersion model; more complex heterogeneities encountered at the field scale were characterized using the superposition of two solute transport equations. Cosolvent and microemulsion flushing solubilize NAPLs by different mechanisms. The modeling results presented here show that nonequilibrium effects influence both of these processes differently. Solubilization of individual constituents by cosolvents was limited by the rate of diffusion or transport of the component through the organic phase, while the rate-limiting step for microemulsification was independent of the NAPL constituent and was likely external to the organic phase. These data indicate that by accounting for field-scale hydrodynamic variability, laboratory-measured nonequilibrium parameters may be used to accurately predict field-scale nonequilibrium NAPL solubilization. Finally, the effects of field-scale media heterogeneity are likely to dominate those of weakly rate-limited dissolution, and accurate characterization of the former may be sufficient for adequate prediction of field-scale NAPL solubilization.     

Removal of polycyclic aromatic hydrocarbons from water by migration into polyethylene

Water was spiked with three polycyclic aromatic hydrocarbons (PAHs) and filled into a steel diffusion chamber. Low-density polyethylene sheet combined of five polyethylene foils was used as a partition in the chamber. Depth of PAHs migration into the sheet was followed for 143 h, using high performance liquid chromatography with selective fluorimetric detection after extraction of PAHs from the foils peeled off. On the basis of the results obtained, the process of PAHs migration into PE was characterised as a one-dimensional diffusion into polyethylene bulk. The diffusion coefficients were calculated for individual compounds using the second Fick law. It was concluded that PAHs are primarily adsorbed on the polyethylene surface with subsequent migration into bulk polymer. Transportation of PAHs through the bulk can be described satisfactorily by Fickian laws of diffusion and is consistent with the theory of the depth adsorption of PAHs in polyethylene.     

Pyrolytic formation of polycyclic aromatic hydrocarbons from sesquiterpenes

The products of the pyrolysis of four sesquiterpenes, β-caryophyllene, α-cedrene, longifolene and valencene, have been examined. Pyrolysis was carried out at 300, 400 and 500°C, the products determined by GC-MS and then examined for similarities and differences using multivariate data analysis. Analysis showed that longifolene was most resistant and caryophyllene least resistant to pyrolysis with cedrene and valencene occupying intermediate positions. While the compounds were largely unchanged at 300°C, polycyclic aromatic hydrocarbons (PAHs) were major components of the pyrolysates at 400 and 500°C. No less than nine of the 16 EPA priority pollutants were present in the pyrolysates at the higher temperatures.     

食品中多环芳烃及卤代多环芳烃的研究进展

综述了多环芳烃及卤代多环芳烃的性质、毒性及国内外食品中的污染情况和研究现状,并对目前的分析测定方法进行了介绍,希望为我国开展食品领域内多环芳烃和卤代多环芳烃的研究提供参考。     

Secondary organic aerosol from photooxidation of polycyclic aromatic hydrocarbons

Secondary organic aerosol (SOA) formation from the photooxidation of five polycyclic aromatic hydrocarbons (PAHs, naphthalene, 1- and 2-methylnaphthalene, acenaphthylene, and acenaphthene) was investigated in a 9-m(3) chamber in the presence of nitrogen oxides and the absence of seed aerosols. Aerosol size distributions and PAH decay were monitored by a scanning mobility particle sizer and a gas chromatograph with a flame ionization detector. Over a wide range of conditions, the aerosol yields for the investigated PAHs were observed to be in the range of 2-22%. The observed evolution of aerosol and PAH decay indicate that light and oxidant sources influence the time required to form aerosol and the required threshold reacted concentration of the PAHs. The SOA yields also were related to this induction period and the hydroxyl radical concentrations, particularly for smaller aerosol loadings (<～6 μg m(-3)). Estimation of SOA production from oxidation of PAHs emitted from mobile sources in Houston shows that PAHs could account for more than 10% of the SOA formed from emissions from mobile sources in this region.     

Aqueous photodegradation of polycyclic aromatic hydrocarbons

Photodegradation of 12 polycyclic aromatic hydrocarbons was studied in aerated pure water, solutions of Suwannee River fulvic acid, and natural waters using polychromatic light (>290 nm). Quantum yields in pure water varied from 3.2 x 10(-5) to 9.2 x 10(-3). No obvious relationships were evident among the quantum yields and molecular properties. Photodegradation rate constants in solutions of Suwannee River fulvic acid or natural waters were largely unchanged compared to rate constants in pure water. Estimates of PAH photodegradation rates in natural waters can thus be obtained employing the quantum yields in pure water, PAH absorption, and solar irradiance. Calculated rate constants for photodegradation in surface waters during the summertime at mid-latitude varied from 3.2 x 10(-3) to 7.6 h(-1).     

Desorption kinetics for field-aged polycyclic aromatic hydrocarbons from sediments

This study considers desorption kinetics for 12 field-aged polycyclic aromatic hydrocarbons (PAHs) desorbing from size- and density-fractionated sediments collected from two locations in the New York/New Jersey Harbor Estuary. Desorption kinetics for PAHs with a log octanol-water partition coefficient greater than 6 were well-described by a one-domain diffusion model that assumes that PAHs are initially uniformly distributed throughout spherical sediment aggregates. PAH hydrophobicity and sediment specific surface area were the parameters most strongly correlated with the magnitude of the observed diffusivity for the one-domain model. For less hydrophobic PAHs, a two-domain desorption model was used also, and the results suggest that a substantial fraction of these field-aged PAHs desorb via a relatively fast macro-mesopore diffusion mechanism. The model-predicted fraction of PAHs in the fast-diffusion regime by compound and sediment was highly correlated with the measured percent PAH desorption in 24 h. The fast-domain diffusivity was 100 times greater than the slow-domain diffusivity, was correlated with both PAH properties and sediment physical and chemical properties, and could be estimated by readily obtainable physical and chemical parameters. In contrast, the slow-domain diffusivity was not significantly correlated with PAH properties. Our results suggest that macro-mesopore diffusion may control mass transport of less-hydrophobic PAHs in estuarine sediments.     

Atmospheric transport and outflow of polycyclic aromatic hydrocarbons from China

A potential receptor influence function (PRIF) model, based on air mass forward trajectory calculations, was applied to simulate the atmospheric transport and outflow of polycyclic aromatic hydrocarbons (PAHs) emitted from China. With a 10 day atmospheric transport time, most neighboring countries and regions, as well as remote regions, were influenced by PAH emissions from China. Of the total annual PAH emission of 114 Gg, 92.7% remained within the boundary of mainland China. The geographic distribution of PRIFs within China was similar to the geographic distribution of the source regions, with high values in the North China Plain, Sichuan Basin, Shanxi, and Guizhou province. The Tarim basin and Sichuan basin had unfavorable meteorological conditions for PAH outflow. Of the PAH outflow from China (8092 tons or 7.1% of the total annual PAH emission), approximately 69.9% (5655 tons) reached no further than the offshore environment of mainland China and the South China Sea. Approximate 227, 71, 746, and 131 tons PAHs reached North Korea, South Korea, Russia-Mongolia region, and Japan, respectively, 2-4 days after the emission. Only 1.4 tons PAHs reached North America after more than 9 days. Interannual variation in the eastward PAH outflow was positively correlated to cold episodes of El Ni?o/Southern Oscillation. However, trans-Pacific atmospheric transport of PAHs from China was correlated to Pacific North America index (PNA) which is associated with the strength and position of westerly winds.     

Outflow of polycyclic aromatic hydrocarbons from Guangdong, southern China

The atmospheric outflow of polycyclic aromatic hydrocarbons (PAHs) from Guangdong, China, a region of high PAH emission, was modeled using a potential receptor influence function (PRIF) probabilistic model which was based on a spatially resolved PAH inventory and air mass forward-trajectory calculations. Photochemical degradation and deposition (dry and wet) of PAHs during atmospheric transport were taken into consideration. On average, 48% of the PAHs (by mass) remained in the atmosphere for a transport period of 5 days, staying within the boundary of the source region. The medium molecular weight PAHs (four rings) were predicted to travel longer distances in the atmosphere than the low (three rings) or high molecular weight PAHs (five rings) because they are less photodegradable than the lower molecular weight, gas-phase PAHs and less likelyto undergo wet and dry depositions than the higher molecular weight, particulate phase PAHs. Under the strong influence of the East Asian monsoons in winter, the predominant outflow pattern of PAHs from Guangdong was to the South China Sea and Southeast Asian countries. In summer, PAHs were transported primarily to northern mainland China. Under particular weather conditions in winter, the PAH-containing air masses were lifted by cold fronts or convection and transported toward the Pacific Ocean by westerly winds. In addition to the distinct seasonality in PAH dispersion and outflow, interannual long-term variation in the outflow is likely influenced by El Ni?o and southern oscillation.     

Emission of polycyclic aromatic hydrocarbons in China

Emission of 16 polycyclic aromatic hydrocarbons (PAHs) listed as U.S. Environmental Protection Agency (U.S. EPA) priority pollutants from major sources in China were compiled. Geographical distribution and temporal change of the PAH emission, as well as emission profiles, are discussed. It was estimated that the total PAH emission in China was 25,300 tons in 2003. The emission profile featured a relatively higher portion of high molecular weight (HMW) species with carcinogenic potential due to large contributions of domestic coal and coking industry. Among various sources, biomass burning, domestic coal combustion, and coking industry contributed 60%, 20%, and 16% of the total emission, respectively. Total emission, emission density, emission intensity, and emission per capita showed geographical variations. In general, the southeastern provinces were characterized by higher emission density, while those in western and northern China featured higher emission intensity and population-normalized emission. Although energy consumption in China went up continuously during the past two decades, annual emission of PAHs fluctuated depending on the amount of domestic coal consumption, coke production, and the efficiency of energy utilization.     

Emissions of polycyclic aromatic hydrocarbons from batch hot mix asphalt plants

This study was set out to assess the characteristics of polycyclic aromatic hydrocarbon (PAH) emissions from batch hot mix asphalt (HMA) plants and PAH removal efficiencies associated with their installed air pollution control devices. Field samplings were conducted on six randomly selected batch HMA plants. For each selected plant, stack flue gas samples were collected from both stacks of the batch mixer (n = 5) and the preheating boiler (n = 5), respectively. PAH samples were also collected from the field to assess PAHs that were directly emitted from the discharging chute (n = 3). To assess PAH removal efficiencies of the installed air pollution control devices, PAH contents in both cyclone fly ash (n=3) and bag filter fly ash (n = 3) were analyzed. Results show that the total PAH concentration (mean; RSD) in the stack flue gas of the batch mixer (354 microg/Nm3; 78.5%) was higher than that emitted from the discharging chute (107 microg/Nm3; 70.1%) and that in the stack flue gas of the preheating boiler (83.7 microg/Nm3; 77.6%). But the total BaPeq concentration of that emitted from the discharging chute (0.950 microg/Nm3; 84.4%) was higher than contained in the stack flue gas of the batch mixer (0.629 microg/Nm3; 86.8%) and the stack flue gas of the preheating boiler (= 0.112 microg/Nm3; 80.3%). The mean total PAH emission factor for all selected batch mix plants (= 139 mg/ton x product) was much higher than that reported by U.S. EPA for the drum mix asphalt plant (range = 11.8-79.0 mg/ton x product). We found the overall removal efficiency of the installed air pollution control devices (i.e., cyclone + bag filter) on total PAHs and total BaPeq were 22.1% and 93.7%, respectively. This implies that the installed air pollution control devices, although they have a very limited effect on the removal of total PAHs, do significantly reduce the carcinogenic potencies associated with PAH emissions from batch HMA plants.     

Emission of oxygenated polycyclic aromatic hydrocarbons from indoor solid fuel combustion

Indoor solid fuel combustion is a dominant source of polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs) and the latter are believed to be more toxic than the former. However, there is limited quantitative information on the emissions of OPAHs from solid fuel combustion. In this study, emission factors of OPAHs (EF(OPAH)) for nine commonly used crop residues and five coals burnt in typical residential stoves widely used in rural China were measured under simulated kitchen conditions. The total EF(OPAH) ranged from 2.8 ± 0.2 to 8.1 ± 2.2 mg/kg for tested crop residues and from 0.043 to 71 mg/kg for various coals and 9-fluorenone was the most abundant specie. The EF(OPAH) for indoor crop residue burning were 1-2 orders of magnitude higher than those from open burning, and they were affected by fuel properties and combustion conditions, like moisture and combustion efficiency. For both crop residues and coals, significantly positive correlations were found between EFs for the individual OPAHs and the parent PAHs. An oxygenation rate, R(o), was defined as the ratio of the EFs between the oxygenated and parent PAH species to describe the formation potential of OPAHs. For the studied OPAH/PAH pairs, mean R(o) values were 0.16-0.89 for crop residues and 0.03-0.25 for coals. R(o) for crop residues burned in the cooking stove were much higher than those for open burning and much lower than those in ambient air, indicating the influence of secondary formation of OPAH and loss of PAHs. In comparison with parent PAHs, OPAHs showed a higher tendency to be associated with particulate matter (PM), especially fine PM, and the dominate size ranges were 0.7-2.1 μm for crop residues and high caking coals and <0.7 μm for the tested low caking briquettes.     

Occurrence of polycyclic aromatic hydrocarbons in smoked cheese

The presence of polycyclic aromatic hydrocarbons (PAH) in smoked cheeses of different origin was studied. The samples were subjected to an initial extraction of fat and an alkaline treatment, extracted with cyclohexane, cleaned up by means of solid-phase extraction tubes, and analyzed by gas chromatography/mass spectrometry (GC/MS) operating in selective ion-monitoring mode (SIM). The results revealed the presence of numerous polycyclic aromatic hydrocarbons in the exterior zone of the samples, some of them with methyl groups. In all cases, the concentrations of compounds of low molecular weight were much higher than those of high molecular weight. Polycyclic aromatic hydrocarbons with varying degrees of carcinogenicity were identified, including benzo(a)pyrene in concentrations, which, although they did not exceed the limit established for this compound in the rind of ripened cheeses, do exceed the limit of 0.03 microg/kg fixed for other foods smoked with smoke flavorings. Significant differences in the number and concentration of PAH in smoked cheese also were observed from rind to interior, the rind being the most contaminated zone.