大气粉尘中常见多环芳烃类化合物的提取及含量测定

采用便携式PM2.5采样器和玻璃纤维滤膜对大气粉尘进行采样,以加压液体萃取、超声波辅助提取和微波辅助提取3种方法对多环芳烃类化合物进行提取,以超高效液相色谱和质谱联用方法进行测定。共检测出16种多环芳烃类化合物,分别为:萘、苊、苊烯、芴、菲、蒽、荧蒽、芘、苯并[a]蒽、■、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、二苯并[a,h]蒽、茚并[1,2,3-c,d]芘和苯并[g,h,i]苝。3种提取方法均可有效提取大气粉尘中的多环芳烃类化合物,加压液体萃取法的提取效率最高、超声波辅助提取法次之、微波辅助提取法最低。超高效液相色谱和质谱连用方法可有效地分析大气粉尘中的多环芳烃类化合物,线性方程的相关系数不低于0.998 3,测定值的相对标准偏差不超过0.80%,检出限不高于0.27 ng/g。     

有机溶剂浸取石油污染土壤中的多环芳烃

采用索氏提取法和气相色谱分析了某炼油厂周边土壤中的多环芳烃的种类及含量,考察了6种有机溶剂对土壤中多环芳烃的浸取效果,探讨了溶剂与溶质溶解度参数差异对浸取效果的影响。结果表明：土壤试样中含有蒽、荧蒽、芘、 、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽和苯并[a]芘8种多环芳烃,其含量分别为4.20,22.05,10.62,4.26,5.54,0.80,0.94,4.18 mg/kg;筛选出二氯甲烷作为土壤中多环芳烃的浸取溶剂;最佳浸取条件为浸取时间10 min、浸取温度30 ℃、溶剂与土壤的液固比5:1（mL/g）、土壤含水量8%,在此条件下,总多环芳烃浸出率为83.0%,各种多环芳烃的浸出率分别为蒽97.8%、荧蒽78.2%、芘99.9%、 98.5%、苯并[a]蒽81.1%、苯并[b]荧蒽47.6%、苯并[k]荧蒽14.8%、苯并[a]芘58.7%。     

Permanganate oxidation of sorbed polycyclic aromatic hydrocarbons

The polycyclic aromatic hydrocarbons (PAH) that contaminate soils at many industrial and government sites are resistant to natural biotic and abiotic degradation processes. The recalcitrant nature of these compounds may require aggressive chemical treatment to effectively remediate these sites. This study was conducted to assess the viability of permanganate oxidative treatment as a method to reduce PAH concentration in contaminated soils. Study results demonstrated a reduction in soil sorbed concentration for a mixture of six PAHs that included anthracene, benzo(a)pyrene, chrysene, fluoranthene, phenanthrene, and pyrene by potassium permanganate (KMnO4) oxidative treatment. The greatest reduction in soil concentration was observed for benzo(a)pyrene, pyrene, phenanthrene, and anthracene at 72.1, 64.2, 56.2, and 53.8%, respectively, in 30 min at a KMnO4 concentration of 160 mM. Minimal reductions in fluoranthene and chrysene concentration were observed at 13.4 and 7.8%, respectively, under the same conditions. A relative chemical reactivity order of benzo(a)pyrene>pyrene>phenanthrene>anthracene>fluoranthene>chrysene towards permanganate ion was observed. Aromatic sextet theory was applied to the degradation results to explain the highly variable and compound-specific chemical reactivity order.     

The Effect of Interaction Between White-rot Fungi and Indigenous Microorganisms on Degradation of Polycyclic Aromatic Hydrocarbons in Soil

White-rot fungi applied for soil bioremediation have to compete with indigenous soil microorganisms. The effect of competition on both indigenous soil microflora and white-rot fungi was evaluated with regard to degradation of polycyclic aromatic hydrocarbons (PAH) with different persistence in soil. Sterile and non-sterile soil was artificially contaminated with ¹⁴C-labeled PAH consisting of three (anthracene), four (pyrene, benz[a]anthracene) and five fused aromatic rings (benzo[a]pyrene, dibenz[a,h]anthracene). The two fungi tested,Dichomitus squalens and Pleurotus ostreatus, produced similar amounts of ligninolytic enzymes in soil, but PAH mineralization by P. ostreatus was significantly higher. Compared to the indigenous soil microflora, P.ostreatus mineralized 5-ring PAH to a larger extent, while the indigenous microflora was superior in mineralizing 3-ring and 4-ring PAH. In coculture the special capabilities of both soil microflora and P. ostreatus were partly restricted due to antagonistic interactions, but essentially preserved. Thus, soil inoculation with P. ostreatus significantly increased the mineralization of high-molecular-weight PAH, and at the same time reduced the mineralization of anthracene and pyrene. Regarding the mineralization of low-molecular-weight PAH, the stimulation of indigenous soil microorganisms by straw amendment was more efficient than application of white-rot fungi.     

Biodegradation of Aliphatic and Aromatic Hydrocarbons: Specificity among Bacteria Isolated from Refinery Waste Sludge

Indigenous microorganisms, enriched and isolated from refinery waste sludge, were observed to possess a broad range of metabolic activities for mixtures of several classes of substrates of petroleum hydrocarbons, such as monoaromatic and polycyclic aromatic hydrocarbons (PAHs) and n- and branched alkanes. Three of the best-growing bacterial isolates selectively enriched with these compounds were identified by 16S rDNA sequencing as belonging to the genera Enterobacter and Ochrobactrum. Two of them, Enterobacter sp. strain EK3.1 and Ochrobactrum sp. strain EK6 utilise a hydrocarbon mixture of the branched alkane 2,6,10,14-tetramethylpentadecane and the PAHs acenaphthylene and acenaphthene. Enterobacter sp. strain EK4 can grow with a mixture of 2,6,10,14-tetramethylpentadecane, toluene, acenaphthylene and acenaphthene as carbon sources. Nucleic acid fingerprint analysis, by terminal restriction fragment length polymorphism (T-RFLP) of the PCR-amplified 16S rRNA genes, of the autochthonous bacterial community in contaminated soil samples showed complex and different community structures under different treatments of refinery waste sludge in landfarm areas. The characteristic peaks of the T-RFLP profiles of the individual, isolated degrading bacteria Enterobacter spp. and Ochrobactrum sp. were detected in the T-RFLP fingerprint of the bacterial community of the four months old treated landfarm soil, suggesting the enrichment of bacteria belonging to the same operational taxonomic units, as well as their importance in degrading activity.     

Occurence and Distribution of Polycyclic Aromatic Hydrocarbons in Ankara Precipitation

Urban atmospheric environment contains many trace organic pollutants that are related to the incomplete fuel combustion in domestic heating, industrial plants and automobile traffic. Removal of these pollutants from the atmosphere takes place through wet and dry deposition as well as chemical transformations. In this study, concentrations of polycyclic aromatic hydrocarbons (PAHs) in wet deposition samples were determined at an urban site of Turkey. Wet and dry deposition samples were collected using Andersen Rain Sampler. The sampler was modified accordingly for the collection of organic pollutants. Collected samples were preconcentrated by using solid phase extraction (SPE) disks and consecutively analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). Among the 13 compounds quantified in this study, anthracene, fluoranthene, and pyrene were found more frequently and at elevated concentrations (202, 271 and 260 ng L^-1 mean concentrations, respectively).Concentrations of PAHs were found to be high in winter period.     

Toxicity and source assignment of polycyclic aromatic hydrocarbons in road dust from urban residential and industrial areas in a typical industrial city in Korea

This study analyzed the toxicity and sources of polycyclic aromatic hydrocarbons (PAHs) in road dust from six representative areas (three urban residential areas and three industrial areas) from a typical industrial city in Korea. The concentrations and the toxicity equivalent concentrations (TEQs) in road dust varied by area, depending on the type of traffic and industrial activities and the PAHs identified. High correlations between the total concentration and the TEQ of PAHs in road dust were found in road dust from both the urban and industrial areas. To identify the sources of PAHs, this study utilized a factor loading method in a principal component analysis, the ratio of PAHs from combustion sources to total PAHs (ΣCOMB to ΣPAH), and bivariate plots of phenanthrene/anthracene (PA/Ant) versus fluoranthene/pyrene (FL/Pyr), and ΣCOMB/ΣPAH versus FL/Pyr in road dust. The identified origin of the PAHs was fuel combustion, including gasoline, diesel, oil, and coal, used in urban and industrial areas.     

多环芳烃污染土壤的微生物修复技术

对生物修复技术中的微生物进行了分类,并阐述了微生物生物降解土壤中多环芳烃（PAHs）的基本原理。在此基础上,分析了国内外微生物生物修复技术的发展概况,采用图示法重点综述了原位处理技术和非原位处理技术的工艺流程,并列举了相应的工程应用实例。     

表面活性剂在多环芳烃污染土壤修复中的应用

介绍了单一表面活性剂（非离子表面活性剂、生物表面活性剂）、阴-非离子混合表面活性剂对多环芳烃的增溶作用、增溶机理及无机离子对表面活性剂增溶能力的影响,综述了化学表面活性剂和生物表面活性剂在污染土壤生物修复中的应用。由于生物表面活性剂具有许多独特的优点,今后应加强生物表面活性剂的开发与应用研究。     

Solvent extraction and soil washing treatment of contaminated soils from wood preserving sites: Bench‐scale studies

Bench‐scale solvent extraction and soil washing studies were performed on soil samples obtained from three abandoned wood preserving sites included in the National Priority List. The soil samples from these sites were contaminated with high levels of polyaromatic hydrocarbons (PAHs), pentachlorophenol (PCP), dioxins, and heavy metals. The effectiveness of the solvent extraction process was assessed using liquefied propane or dimethyl ether as solvents over a range of operating conditions. These studies have demonstrated that a two‐stage solvent extraction process using dimethyl ether as a solvent at a ratio of 1.61 per kg of soil could decrease dioxin levels in the soil by 93.0 to 98.9 percent, and PCP levels by 95.1 percent. Reduction percentages for benzo(a)pyrene (BaP) potency estimate and total detected PAHs were 82.4 and 98.6 percent, respectively. Metals concentrations were not reduced by the solvent extraction treatment. These removal levels could be significantly improved using a multistage extraction system. Commercial scale solvent extraction using liquefied gases costs about $220 per ton of contaminated soil. However, field application of this technology at the United Creosote site, Conroe, Texas, failed to perform to the level observed at bench scale due to the excessive foaming and air emission problem. Soil washing using surfactant solution and wet screening treatability studies were also performed on the soil samples in order to assess remediation strategies for sites. Although aqueous phase solubility of contaminants seemed to be the most important factor affecting removal of contaminants from soil, surfactant solutions (3 percent by weight) having nonionic surfactants with hydrophile‐lipophile balance (HLB) of about 14 (Makon‐12 and Igepal CA 720) reduced the PAH levels by an average of 71 percent, compared to no measurable change when pure deionized water was used. Large fractioza of clay and silt (<0.06mm), high le!ezielsof orgaizic contami‐ nants and hzimic acid can makesoil washing less applicable.     

Use of fungal technology in soil remediation: A Case Study

Two white rot fungi Irpex lacteus and Pleurotus ostreatus and a PAH-degrading bacterial strain of Pseudomonas putida were used as inoculum for bioremediation of petroleum hydrocarbon-contaminated soil from a manufactured-gas-plant-area. Also two cocultures comprising a fungus with Pseudomonas putida were applied. After 10-week treatment out of 12 different PAHs, concentration of phenanthrene, anthracene, fluoranthene and pyrene decreased up to 66%. The ecotoxicity of the soil after bioremediation did not reveal any effect on the survival of Daphnia magna, a crustacian. However, the toxic effect on seed germination of plant Brassica alba and oxidoreductase activity of bacterium Bacillus cereus decreased after 5 and 10 weeks of treatment.     

Land treatment and the toxicity response of soil contaminated with wood preserving waste

Soils contaminated with wood preserving wastes, including pentachlo-rophenol (PCP) and creosote, are treated at field-scale in an engineered prepared-bed system consisting of two one-acre land treatment units (LTUs). The concentration of selected indicator compounds of treatment performance included PCP, pyrene, and total carcinogenic polycyclic aromatic hydrocarbons (TCPAHs) was monitored in the soil by taking both composited soil samples at multiple points in time, and discrete soil samples at two points in time. The mean concentration of the indicator compounds and the 95-percent confidence interval (CI) of the composite and discrete samples agreed relatively well, and first-order degradation rate kinetics satisfactorily represented the mean chemical concentration loss of indicator compounds in the LTU. Toxicity of the soil, as measured by Microtox^TM assay of the soil extracts, indicated that toxicity reduction corresponded with indicator compound disappearance. No toxicity effects were observed with time in treated layers of soil (lifts) buried beneath highly contaminated lifts of newly applied soil. This indicated that vertical migration of soluble contaminants from such lifts had little effect on the microbial activity in the underlying treated soil.     

Occurrence of organic pollutants in recovered soil fines from construction and demolition waste

The objective of this study was to characterize recovered soil fines from construction and demolition (C&D) waste recycling facilities for trace organic pollutants. Over a period of 18 months, five sampling trips were made to 14 C&D waste recycling facilities in Florida. Screened soil fines were collected from older stockpiles and newly generated piles at the sites. The samples were analyzed for the total concentration (mg/kg) of a series of volatile organic compound (VOCs) and semi-volatile organic compounds (semi-VOCs). The synthetic precipitation leaching procedure (SPLP) test was also performed to evaluate the leachability of the trace organic chemicals. During the total analysis only a few volatile organic compounds were commonly found in the samples (trichlorofluoromethane, toluene, 4-isopropyltoluene, trimethylbenzene, xylenes, and methylene chloride). A total of nine VOCs were detected in the leaching test. Toluene showed the highest leachability among the compounds (61.3-92.0%), while trichlorofluoromethane, the most commonly detected compound from both the total and leaching tests, resulted in the lowest leachability (1.4-39.9%). For the semi-VOC analysis, three base-neutral semi-VOC compounds (bis(2-ethylhexyl)phthalate, butyl benzyl phthalate, and di-n-butyl phthalate) and several PAHs (acenaphthene, pyrene, fluoranthene, and phenanthrene) were commonly detected in C&D fines samples. These compounds also leached during the SPLP leaching test (0.1-25%). No acid extractable compounds, pesticides, or PCBs were detected. The results of this study were further investigated to assess risk from land applied recovered soil fines by comparing total and leaching concentrations of recovered soil fines samples to risk-based standards. The results of this indicate that the organic chemicals in recovered soil fines from C&D debris recycling facilities were not of a major concern in terms of human risk and leaching risk to groundwater under reuse and contact scenarios.     

Assessing the potential of using phytoremediation for pyrene‐contaminated soils

Forage crop species representing two biologically distinct families (legumes and grasses) were evaluated on soil spiked with 100 mg/kg of pyrene to determine the potential effectiveness of the rhizospheres of these plants for phytoremediation. In this experiment, pyrene dissipation could not be attributed to the presence of plants. Pyrene dissipation was also not related to rhizosphere biological activity, such as microbial counts and enzyme activity. Planting with reed canarygrass and switchgrass significantly increased the microbial counts in soil; however, the differences in the microbial counts were not correlated to the levels of pyrene dissipation. Reed canarygrass rhizosphere had significantly higher dehydrogenase activity compared to the switchgrass rhizosphere, but this difference in soil dehydrogenase activity was not related to pyrene dissipation. In general, the use of plants was not effective in causing pyrene transformation; however, the presence of vegetation on polycyclic aromatic hydrocarbon–contaminated soils could play a significant role in limiting the spread of contaminants (erosion, leaching) and enhancing ecosystem restoration. © 2004 Wiley Periodicals, Inc.     

过氧化钙降解有机污染物研究进展

CaO2具有很好的稳定性,可在水和土壤中逐步分解生成H2O2成为氧化反应的氧化剂,已作为H2O2的替代物用于环保领域的研究中.介绍了CaO2的作用机理,综述了CaO2用于处理含卤代物、染料、抗生素、苯系物等废水的研究进展,以及CaO2用于治理含石油烃、多环芳烃、苯系物和农药的污染土壤的研究进展.提出未来的研究方向:充分...     

Remediation of Soil and Ground Water Contaminated with PAH using Heat and Fe(II)-EDTA Catalyzed Persulfate Oxidation

The feasibility of degrading 16 USEPA priority polycyclic aromatic (PAH) hydrocarbons (PAHs) with heat and Fe(II)-EDTA catalyzed persulfate oxidation was investigated in the laboratory. The experiments were conducted to determine the effects of temperature (i.e. 20 ^∘C, 30 ^∘C and 40 ^∘ C) and iron-chelate levels (i.e., 250 mg/L-, 375 mg/L- and 500 mg/L-Fe(II)) on the degradation of dissolved PAHs in aqueous systems, using a series of amber glass jars as the reactors that were placed on a shaker inside an incubator for temperature control. Each experiment was run in duplicate and had two controls (i.e., no persulfate in systems). Samples were collected after a reaction period of 144 hrs and measured for PAHs, pH and sodium persulfate levels. The extent of degradation of PAHs was determined by comparing the data for samples with the controls. The experimental results showed that persulfate oxidation under each of the tested conditions effectively degraded the 16 target PAHs. All of the targeted PAHs were degraded to below the instrument detection limits (∼4 μ/L) from a range of initial concentration (i.e., 5 μ/L for benzo(a)pyrene to 57 μ/L for Phenanthrene) within 144 hrs with 5 g/L of sodium persulfate at 20 ^∘ C, 30 ^∘C and 40 ^∘C. The data indicated that the persulfate oxidation was effective in degrading the PAHs and that external heat and iron catalysts might not be needed for the degradation of PAHs. The Fe(II)-EDTA catalyzed persulfate also effectively degraded PAHs in the study. In addition, the data on the variation of persulfate concentrations during the experiments indicated that Fe(II)-EDTA accelerated the consumption of persulfate ions. The obtained degradation data cannot be used to evaluate the influence of temperature and Fe(II) levels on the PAH degradation because the PAHs under each of the tested conditions were degraded to below the instrument detection limit within the first sampling point. However, these experiments have demonstrated the feasibility of degrading PAHs in aqueous systems with persulfate oxidation. Additional tests are being conducted to evaluate the effectiveness of treating PAHs in soils and obtaining the rate of degradation of PAHs with persulfate oxidation. Two sets of laboratory experiments were conducted to evaluate the ability of sodium persulfate in oxidizing real world PAH-contaminated soils collected from a Superfund site in Connecticut. The first set of soil sample were treated only with persulfate and to the second batch, mixture of persulfate and Fe(II)-EDTA solutions were added. The results of the second test showed that within 24 hours, 75% to 100% of the initial concentrations of seven PAH compounds detected in the soil samples were degraded by sodium persulfate mixed with FE(II)-EDTA.     

萘降解菌的筛选及其对多环芳烃的降解

从柴油污染土壤中筛选分离出一株萘降解菌N-3,进行了菌种鉴定及萘双加氧酶基因(nah)验证,并考察了该菌对不同种类多环芳烃(PAHs)的降解能力及降解过程中脱氢酶活性的变化。实验结果表明:该菌为铜绿假单胞菌(Pseudomonas aeruginosa),含有nah基因;当分别对液体培养基中质量浓度为50 mg/L的萘、菲、蒽、芘、芴降解84 h时,菌株N-3对萘、菲、蒽、芘、芴的降解率分别为28.81%,34.83%,36.65%,27.50%,23.47%。菌株N-3的脱氢酶活性与其对不同PAHs的降解率呈一定的正相关性。该菌不仅能有效降解萘,且对其他种类PAHs也有一定降解作用。     

The efficacy of an oxidation pond in mineralizing some industrial waste products with special reference to fluorene degradation: a case study

The efficacy of the oxidation pond on the outskirts of the 10th of Ramadan, the main industrial city, in Egypt was examined. Samples of wastewater collected from the inlet and the outlet were screened for some priority pollutants. Acenaphthene and fluorene were the most frequently detected polycyclic aromatic hydrocarbons, while dimethyl phthalate was the most frequently detected phthalate ester. The spectrum of pollutants, their concentrations and frequencies were similar in the inlet and the outlet, indicating an inferior mineralization capability of the pond. Several degradative bacterial strains were isolated from the pond and grown on M56 minimal media supplemented with different pollutants as the carbon source. The efficacy of pure and mixed cultures to break down fluorene, the most frequently detected pollutant was examined. Fluorene degradation was fast in the first 10 days, then followed by a slow phase. Mixed culture had a higher rate of fluorene degradation in comparison to pure cultures. High performance liquid chromatography analysis of fluorene degradation showed three degradative metabolites. But GC/MS analysis detected one compound, identified as acetamide. The present work has indicated the poor efficacy of the pond. Lack of primary treatment of industrial effluent at factory level, coupled with shock loads of toxicants that may damage the microorganisms and their degradative capabilities are presumably main factors behind such inferior performance. Moreover, the type of pollutants discharged into the pond tend to fluctuate and change depending on the rate from the factories discharge and work shifts. Such irregular feeding of persistent pollutants may have led to a wash out of specialized strains of bacteria capable to degrade such persistent pollutants.     

A Study of the Use of Alfalfa (Medicago sativa L.) for the Phytoremediation of Organic Contaminants in Soil

This article presents the results of a study that was conducted to determine the effectiveness of using alfalfa (Medicago sativa L.) to enhance the phytoremediation of three different types of chemical contaminants. The chemicals studied were trinitrotoluene (TNT), the polycyclic aromatic hydrocarbon (PAH) pyrene, and the polychlorinated biphenyl (PCB) Aroclor 1248. Experiments were conducted using soils that contained high and low organic matter content. The results indicated that recoveries of pyrene and TNT from soil were highly dependent on the soil organic matter content, while the recovery of PCB was not. Significantly low levels of pyrene and TNT were recovered from all treatments in the soil with 6.3 percent organic matter content compared to recovery levels found in soil with 2.6 percent organic matter. The presence of alfalfa plants had a significant effect on the transformation of TNT and PCB in the low organic matter content soil only and had no effect on the fate of pyrene. In the low organic matter soil, only 15 percent and 17 percent of the initial TNT and PCB levels, respectively, were transformed in the unplanted control soils compared to 66 percent and 77 percent in the alfalfa planted pots. In both soil types, pyrene dissipation could not be attributed to the presence of alfalfa plants. Overall, it was concluded that under high soil organic matter conditions, adsorption and covalent binding to the soil organic matter appeared to be the dominant force of pyrene and TNT removal. The effectiveness of using alfalfa to enhance PCB and TNT transformations was more significant in the lower organic matter soil; thus phytoremediation had a greater effect in soils with lower organic matter content. © 2001 John Wiley & Sons, Inc.     

Validation of petroleum hydrocarbon extraction methodologies

Solvents, the extraction time and extraction method, influence the quantification of polycyclic aromatic hydrocarbons (PAHs) in soil. This paper emphasizes the importance of establishing, and being consistent in the application of, a vigorous extraction, particularly for commercial laboratories that handle samples of soil in batches, at different times, from a single site investigation or remediation process. It is important that laboratories are aware of the performance of their soil contaminant extraction procedures. Equally important is that analytical laboratories communicate to you, the practitioner and user of the data, what variables there are in soil contaminant extractions, whether it be PAH, fuel, or recalcitrant organics, and how these can impact on the final data quality.