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.     

Cyclodextrin enhanced biodegradation of polycyclic aromatic hydrocarbons and phenols in contaminated soil slurries

This work aimed to evaluate the relative contribution of soil catabolic activity, contaminant bioaccessibility, and nutrient levels on the biodegradation of field-aged polycyclic aromatic hydrocarbons and phenolic compounds in three municipal gas plant site soils. Extents of biodegradation achieved, in 6 week-long soil slurry assays, under the following conditions were compared: (i) with inoculation of catabolically active PAH and phenol-degrading microorganisms, (ii) with and without hydroxypropyl-beta-cyclodextrin supplementation (HPCD; 100 g L(-1)), and finally (iii) with the provision of additional inorganic nutrients in combination with HPCD. Results indicated no significant (p < 0.05) differences between biodegradation endpoints attained in treatments inoculated with catabolically active microorganisms as compared with the uninoculated control. Amendments with HPCD significantly (p < 0.05) lowered biodegradation endpoints for most PAHs and phenolic compounds. Only in one soil did the combination of HPCD and nutrients consistently achieve better bioremediation endpoints with respect to the HPCD-only treatments. Thus, for most compounds, biodegradation was not limited by the catabolic activity of the indigenous microorganisms but rather by processes resulting in limited availability of contaminants to degraders. It is therefore suggested that the bioremediation of PAH and phenol impacted soils could be enhanced through HPCD amendments. In addition, the biodegradability of in situ and spiked (deuterated analogues) PAHs following 120 days aging of the soils suggested that this contact time was not sufficient to obtain similar partitions to that observed for field-aged contaminants; with the spiked compounds being significantly (p < 0.05) more available for biodegradation.     

天然生育酚中痕量多环芳烃脱除工艺的研究

采用活性炭吸附法脱除天然生育酚中的多环芳烃（PAHs）,考察了脱除溶剂、活性炭种类、搅拌时间、温度、活性炭用量、脱除次数对多环芳烃脱除率的影响。结果表明,用乙醇（分析纯）溶剂溶解生育酚（液固比为5：1）,加入10％的HC-2型活性炭,在20℃下搅拌45min,对PAHs可以达到较好的脱除效果（对轻PAHs的脱除率达到48％以上,对重PAHs的脱除率达到98％以上,对总PAHs的脱除率达到88％以上）,重PAHs的残留量为5．22ng／g,轻PAHs的残留量为86．22ng／g。     

Mechanisms of the aqueous photodegradation of polycyclic aromatic hydrocarbons

The role of O2 and photoionization as well as the involvement of polycyclic aromatic hydrocarbon (PAH) cation radicals (P+) in the photodegradation of nine PAHs was examined. Photodegradation quantum yields for all PAHs increased with increasing O2 concentration, illustrating the key role of O2 in the photodegradation mechanism. In the presence of a series of electron donors (to P+), the photodegradation rate constants of most PAHs were largely unaffected at low O2 concentrations (< or = 250 microM), indicating that P+ is not extensively produced. However, at higher O2 concentrations (up to 1.2 mM), the presence of the donors substantially lowered photodegradation rates for most PAHs, indicating that P+ is produced and is arising from O2 reaction with the excited singlet state. Because little P+ was detected at low O2 concentrations and, further, because degradation rates were not enhanced in the presence of N2O, we conclude that photoionization is unimportant. With some exceptions, photodegradation can proceed through reaction of O2 with both excited singlet and triplet states of the PAHs. Our results indicate that photodegradation via the excited singlet state occurs primarily through electron transfer to O2, whereas degradation via the triplet occurs predominately through a direct reaction of O2 with the PAH within the collision complex.     

A novel cloud-point extraction process for preconcentrating selected polycyclic aromatic hydrocarbons in aqueous solution

A novel but simple cloud-point extraction (CPE) process is developed to preconcentrate the trace of selected polycyclic aromatic hydrocarbons (PAHs) with the use of the readily biodegradable nonionic surfactant Tergitol 15-S-7 as extractant. The concentrations of PAHs, mixtures of naphthalene and phenanthrene as well as pyrene, in the spiked samples were determined with the new CPE process at ambient temperature (23 degrees C) followed by high performance liquid chromatography(HPLC) with fluorescence detection. More than 80% of phenanthrene and pyrene, respectively, and 96% of naphthalene initially present in the aqueous solutions with concentrations near or below their aqueous solubilities were recovered using this new CPE process. Importantly Tergitol 15-S-7 does not give any fluorometric signal to interfere with fluorescence detection of PAHs in the UV range. No special washing step is, thus, required to remove surfactant before HPLC analyses. Different experimental conditions were studied. The optimum conditions for the preconcentration and determination of these selected PAHs at ambient temperature have been established as the following: (1) 3 wt% surfactant; (2) addition of 0.5 M Na2SO4; (3) 10 min for equilibration time; and (4) 3000 rpm for centrifugal speed with duration of 10 min.     

Removal of polycyclic aromatic hydrocarbons by low density polyethylene from liquid model and roasted meat

Low density polyethylene (LDPE) was used to remove polycyclic aromatic hydrocarbons (PAHs) from liquid media and roasted meat by sorption. Three liquid models and five carcinogenic PAHs were employed to monitor the sorption process, and amounts of chemicals were determined by GC-FID. More than 50% of the total adsorption occurred within 24 h for the selected PAHs in the three model systems. The water–oil system yielded the highest PAHs removal by LDPE; and the system containing phospholipid resisted the diffusion and resulted in the least adsorption among three models. Certain residual PAHs in the LDPE were significantly decreased to a range of 70.8–84.0% after 3 h of UV radiation, and benzo(a)pyrene was the most sensitive to UV among these PAHs. Removal of PAHs in roasted meat packaged under vacuum was achieved, and potent contamination by the PAHs in the LDPE may be avoided by subsequent UV irradiation.     

Reaction of polycyclic aromatic hydrocarbons adsorbed on silica in aqueous chlorine

The reaction of polycyclic aromatic hydrocarbons (PAHs) previously adsorbed on silica gel or diatomaceous earth with sodium hypochlorite was carried out to elucidate their reactivity to aqueous chlorine. It was demonstrated that the PAHs adsorbed on silica reacted more rapidly than the PAHs themselves in water, leading to the formation of many chlorinated and oxidized derivatives. A similar reaction in the presence of potassium bromide was found to preferentially produce corresponding brominated derivatives. These reactions seem to proceed through PAHs adsorbed on the silica surface and halogenating agents, the electrophilicity of which may be raised by the catalytic effect of the silanol group of the silica surface. These findings from the environmental viewpoint suggest that the reaction of hydrophobic compounds adsorbed on sediment cannot be neglected.     

Electron-beam treatment of aromatic hydrocarbons that can be air-stripped from contaminated groundwater. 1. Model studies in aqueous solution

As a model for the electron-beam degradation of volatile aromatics (benzene, toluene, ethylbenzene, xylenes, BTEX) in groundwater strip gas, to be reported in Part 2, the gamma-radiolysis of benzene has been studied in aqueous solutions. Addition of *OH to the aromatic ring gives rise to hydroxycyclohexadienyl radicals which either dimerize or disproportionate. The various dimers undergo acid-catalyzed water elimination yielding biphenyl. Phenol is formed upon disproportionation directly, but also via dihydroxycyclohexadiene which subsequently undergoes acid-catalyzed water elimination. Co-radiolysis of benzene with nitrite generates *NO2 in addition to the hydroxycyclohexadienyl radical. These not only interact with one another (product: nitrobenzene via nitro-hydroxycyclohexadienes) but the *NO2 radical is also capable of abstracting cyclohexadienylic hydrogens. This reaction leads to the formation of 2- and 4-nitrophenol and to further nitrated products that were not identified. These are suggested to be formed in an analogous reaction of *NO2 with the hydroxycylohexadienyl dimers. The effect of O2 on these reactions and the relevance for the gas-phase radiolysis of BTEX is discussed.     

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.     

Kinetics of sunflower oil contamination with polycyclic aromatic hydrocarbons from contaminated recycled low density polyethylene film

The possibility of food contamination with polycyclic aromatic hydrocarbons (PAHs) by rediffusion from polyethylene film made of contaminated recycled polyethylene (PE) was tested. PE was contaminated with PAHs by diffusion from water medium spiked with fluoranthene (FI), pyrene (Py), and benzo(a)pyrene (BaP). The PE was recycled by heating at 150°C for 10 min. The recycling process did not affect the PAH concentration in PE. From the recycled PE, a PE film was made and rediffusion of PAHs from the PE film into a sunflower oil was followed for 600 h at 24°C. Diffusion of PAHs into the oil demonstrated the potential of PAH-contaminated PE as a source of contamination of food. The PAH concentration in vegetable oil was linearly dependent on the square root of the storage time. A kinetic equation for PAH rediffusion from PE film into the oil is proposed.     

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。     

吸附法脱除油脂中多环芳烃的效果研究

以花生油为原料,以吸附剂种类、吸附剂用量、吸附温度和吸附时间为单因素试验考察因素,通过单因素试验和正交试验研究吸附法对油脂中多环芳烃的脱除效果及最佳脱除条件。结果表明,不同种类吸附剂对花生油中多环芳烃的脱除效果依次为:Norit-8015活性炭WY2号活性炭WY1号活性炭Kermel活性炭活性白土凹凸棒土。综合考虑对花生油中B(a)P、HPAHs、PAH4、LPAHs和PAH16的脱除率以及对花生油香味的保留和生产成本,优化的脱除条件为:WY2号活性炭用量1.0%,吸附时间35min,吸附温度110℃。在此条件下,花生油中B(a)P、HPAHs、PAH4、LPAHs及PAH16的残留量分别为0.06、0.69、1.74、95.11μg/kg及80.90μg/kg,脱除率分别为99.74%、99.28%、98.65%、85.75%及89.41%,若仅考虑B(a)P、PAH4的残留量达到欧盟标准(分别为≤2μg/kg和≤10μg/kg),WY2号活性炭的添加量为0.5%就可满足要求,此时B(a)P和PAH4的残留量分别为0.53μg/kg和6.64μg/kg,脱除率分别为97.79%和94.86%。     

Enhanced diffusion of polycyclic aromatic hydrocarbons in artificial and natural aqueous solutions

Uptake of hydrophobic organic compounds into organisms is often limited by the diffusive transport through a thin boundary layer. Therefore, a microscale diffusion technique was applied to determine the diffusive mass transfer of 12 polycyclic aromatic hydrocarbons through water, air, surfactant solutions, humic acid solutions, aqueous soil and horse manure extracts, digestive fluid of a deposit-feeding worm, and root exudates from willow plants. In most cases the diffusive mass transfer of PAHs was much higher through the tested media than through water, and the enhancement factors increased with increasing hydrophobicity of the PAHs. The diffusive flux of benzo[a]pyrene was for instance enhanced 74 times through gut fluid of a deposit-feeding worm when compared to water. These findings demonstrate that a wide variety of dissolved organic carbon (DOC) at environmental levels can enhance diffusive mass transfer in various transport scenarios. The diffusive uptake of PAHs into sediment dwelling organisms is particularly efficient within the gut and at direct contract with the sediment matrix. Bioremediation might be enhanced bythe addition of auxiliary agents that enhance diffusive mass transfer. Enhanced diffusion needs also to be considered in dynamic transport models and for the operation and calibration of passive sampling techniques.     

Adsorption of polycyclic aromatic hydrocarbons by carbon nanomaterials

Carbon nanomaterials are novel manufactured materials, having widespread potential applications. Adsorption of hydrophobic organic compounds (HOCs) by carbon nanomaterials may enhance their toxicity and affect the fate, transformation, and transport of HOCs in the environment. In this research, adsorption of naphthalene, phenanthrene, and pyrene onto six carbon nanomaterials, including fullerenes, single-walled carbon nanotubes, and multiwalled carbon nanotubes was investigated, which is the first systematic study on polycyclic aromatic hydrocarbons (PAHs) sorption by various carbon nanomaterials. All adsorption isotherms were nonlinear and were fitted well by the Polanyi-Manes model (PMM). Through both isotherm modeling and constructing "characteristic curve", Polanyi theory was useful to describe the adsorption process of PAHs by the carbon nanomaterials. The three fitted parameters (Q0, a, and b) of PMM depended on both PAH properties and the nature of carbon nanomaterials. For different PAHs, adsorption seems to relate with their molecular size, i.e., the larger the molecular size, the lower the adsorbed volume capacity (Q0), but higher a and b values. For different carbon nanomaterials, adsorption seems to relate with their surface area, micropore volume, and the volume ratios of mesopore to micropore. Quantitative relationships between these sorbent properties and the estimated parameters of PMM were obtained. These relationships may represent a first fundamental step toward establishing empirical equations for quantitative prediction of PAH adsorption by carbon nanomaterials and possibly other forms of carbonaceous (geo-) sorbents, and for evaluating their environmental impact. In addition, high adsorption capacity of PAHs by carbon nanotubes may add to their high environmental risks once released to the environment, and result in potential alteration of PAHs fate and bioavailability in the environment.     

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.