溶解有机质在土壤及沉积物吸附多环芳烃类有机污染物过程中的作用研究

研究了采自官厅水库及周围水域的 6种土壤及沉积物样品对多环芳烃类有机化合物———萘、菲、芘的吸附特性 ,应用1H NMR对这 6种土壤及沉积物样品中的溶解有机质的化学组成进行了的测定 ,发现溶解有机质中芳香族和非极性脂肪族化合物的含量与Freundlich吸附容量 (K′f)之间存在着密切关系 ,Freundlich吸附指数 (n)随着溶解有机质中极性基团的增多而降低 ,但是极性芳香族成分在吸附过程中主要充当有机溶剂相 .另外 ,吸附质的化学特性对吸附也有重要影响 ,logK′f 与logKow(Kow为辛醇 水分配系数 )之间存在着线性关系 .依据溶解腐殖质的两性特征及上述结论建立了一种快速吸附模型 。

The expression of PAH-DNA adducts in lung tissues of Xuanwei female lung cancer patients

Objective:The coal-fired pollution in Xuanwei area has been considered to be local main reason for high incidence of female lung cancers.The aim of the study was to investigate the expression of PAH-DNA adducts in lung tissues of Xuanwei female lung cancer patients, and to explore the relationship between the large number of coal-fired pollution PAHs materials and the high incidence of Xuanwei female lung cancers.Methods:We totally collected each 20 cases of Xuanwei female lung cancer patients, Xuanwei male lung cancer patients, non-Xuanwei female lung cancer patients and collected each 10 cases of Xuanwei, non-Xuanwei female patients with benign lung lesions.The cancer tissues, adjacent cancer tissues and normal lung tissues were collected in lung cancer patients and only the normal tissues were collected in benign lung lesion patients.There were total 80 cases and 200 tissues.Using immunofluorescence, we detected the expression of PAH-DNA adducts in each group.Image pro-plus 6.0 software was used to analyze the images and did part quantified analysis.SPSS 13.0 statistical software was used to analyze the data.Results:The positive expressions of PAH-DNA adducts in lung cancer tissues, adjacent cancer tissues and normal lung tissues of Xuanwei female lung cancer patients were 90%, 80% and 65%, respectively.They were higher than the positive expressions of PAH-DNA adducts in Xuanwei male lung cancer patients (35%, 30% and 30%) and non-Xuanwei female lung cancer patients (20%, 15% and 10%; P<0.01).The expression of PAH-DNA adducts in lung tissues of Xuanwei female benign lung lesion patients (70%) was higher than that in non-Xuanwei female benign lung lesion patients (10%).With the direction changing from cancer tissues, adjacent cancer tissues to normal lung tissues, the expression of PAH-DNA adducts was decreased but had no statistical difference (P>0.05).Conclusion:The expression of PAH-DNA adducts in lung tissues of Xuanwei females was higher than that in Xuanwei males and non-Xuanwei females.

Polycyclic aromatic hydrocarbon formation under simulated coal seam pyrolysis conditions

Coal seam pyrolysis occurs during coal seam fires and during underground coal gasification. This is an important source of polycyclic aromatic hydrocarbon （PAH） emission in China. Pyrolysis in a coal seam was simulated in a tubular furnace. The 16 US Environmental Protection Agency priority controlled PAHs were analyzed by HPLC. The effects of temperature, heating rate, pyrolysis atmosphere, and coal size were investigated. The results indicate that the 3-ring PAHs AcP and AcPy are the main species in the pyrolysis gas. The 2-ring NaP and the 4-ring Pyr are also of concern. Increasing temperature caused the total PAH yield to go through a minimum. The lowest value was obtained at the temperature of 600℃. Higher heating rates promote PAH formation, especially formation of the lower molecular weight PAHs. The typical heating rate in a coal seam, 5 ℃/min, results in intermediate yields of PAHs. The total PAHs yield in an atmosphere of N2 is about 1.81 times that seen without added N2, which indicates that an air flow through the coal seam accelerates the formation of PAHs. An increase in coal particle size reduces the total PAHs emission but promotes the formation of 5- and f-ring PAHs.

Levels and statistical analysis of aerosol phase PAHs over Qingdao alongshore

Atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured during various seasons at six different cities/locations in Qingdao alongshore. The annual average PAHs concentration ranged from 16 ng/m3 (at a clean com- pared site) to 308 ng/m3 (in an industry site). The average total particulate PAHs concentration was 74.5 ng/m3 with a higher concentration of particulate PAHs in winter. Based on a year-round dataset, the sources of PAHs in the air of Qingdao were drawn by principal factor analysis and correlation analysis. The results indicated that vehicle emissions and oil burning were the main source of PAHs in Qingdao alongshore.

The Study of Pollution of PAHs （Polycyclic Aromatic Hydrocarbons） in AI-Hilla River, Iraq by Using Bioindicator Freshwater Crab （Sesarma boulengeri Caiman）

The present study was used freshwater Crab （Sesarma boulengeri Caiman） as bioindicator to measured the PAHs levels in AI-Hilla River, Iraq, during the period from March 2010 to February 2011. Crab samples were collected from two sites on the AI-Hilla River. Sixteen of PAils compounds were identified seasonally in these samples. High mean value was （72.06 μg/g）, recorded by Dibenzo （a, h） anthracene （DbA） in Site 1 and low mean value was （0.36 μg/g） recorded by Anthracene （Ant） in Site 2. The study showed a clear variation in PAHs concentration independent from the seasons and locations. Site 1 recorded high value of HMW （high molecular weight） and LMW （low molecular weight） more than Site 2. The present study revealed that all PAHs compounds were from Pyrogenic Origin. Seven carcinogenic PAHs （cPAHs） were recorded in crab tissues that were collected from the AI-Hilla River. The TEF （toxicity equivalency factor） was calculated to toxicity equivalent crab concentration. From the results, the fresh water Crab Sesarma boulengeri is a good bioindicator to water pollution by PAHs.

CARBONIZED FIBROUS RESIN AS A NEW SORBENT FOR SAMPLING POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) IN AMBIENT AIR

A new sampling method of ambient air analysis using carbonized fibrous resin as a sorbent for polycyclic aromatic hydrocarbons (PAHs) was reported. The physical and chemical properties of the carbonized fibrous resins were measured. The sample pretreatment with ultrasonic extraction and subsequent clean-up elution through a silica gel column was optimized. The suitable ultrasonic extraction conditions were selected as follows: resin weight was 1.5 g, ultrasonic extraction time 20 min, volume of extraction solvent 100 ml and extraction operation times 2~3. The concentrated extractable organic matter was submitted to next step of clean-up procedure of adsorption chromatography on silica gel column/n-hexane and a mixture of dichloromethene:n-hexane solution 2:3 (v/v). The PAHs fractions in the real samples from Changzhou, China were particularly analyzed using GC-MS data system and the data of mass spectra, retention times and scan numbers of the real samples were compared with that of the standards of 16 PAHs listed by the US EPA as 損riority pollutants?of the environment. The analysis of the real samples indicates that the carbonized fibrous resin is a good sorbent. The pretreatment of samples of ambient air with carbonized fibrous resin as a sorbent for PAHs is proved to be reliable and might be used for the procedure of the determination of PAHs in atmospheric environment.

Marine Bacterial Biofilms in Bioremediation of Polycyclic Aromatic Hydrocarbons(PAHs) Under Terrestrial Condition in a Soil Microcosm

Polycyclic aromatic hydrocarbons （PAHs） in soil retain for a quite long period due to their hydrophobicity and aggregation properties. Biofilm-forming marine bacterial consortium （named as NCPR）, composed of Stenotrophomonas acidaminiphila NCW702, Alcaligenes faecalis NCW402, Pseudomonas mendocina NR802, Pseudornonas aeruginosa N6P6, and Pseudomonas pseudoalcaligenes NP103, was used for the bioremediation of PAHs in a soil microcosm. Phenanthrene and pyrene were used as reference PAHs. Parameters that can affect PAH degradation, such as chemotaxis, solubility of PAHs in extracellular polymeric substances （EPS）, and catechol 2,3-dioxygenase （C230） activity, were evaluated. P. aeruginosa N6P6 and P. pseudoalcaligenes NP103 showed chemotactic movement towards both the reference PAHs. The solubility of both the PAHs was increased with an increase in EPS concentration （extracted from all the 5 selected isolates）. Significantly （P 〈 0.001） high phenanthrene （70.29%） and pyrene （55.54%） degradation was observed in the bioaugmented soil microcosm. The C230 enzyme activity was significantly （P 〈 0.05） higher in the bioaugmented soil mi- crocosm with phenanthrene added at 173.26 ± 2.06 nmol rain-1 mg-1 protein than with pyrene added at 61.80 ± 2.20 nmol min-1 mg-1 protein. The C230 activity and gas chromatography-mass spectrometer analyses indicated catechol pathway of phenanthrene metabolism. However, the metabolites obtained from the soil microcosm added with pyrene revealed both the catechol and phthalate pathways for pyrene degradation.

Biotransformation of nitro-polycyclic aromatic compounds by vegetable and fruit cell extracts

Extracts from various vegetables and fruits were investigated for their abilities to reduce nitro-polycyclic aromatic hydrocarbons （NPAHs）. The extracts from grape and onion exhibited an interesting selectivity, yielding corresponding hydroxylamines or amines as major products under mild conditions of 30 ℃ and pH 7.0. Grape extracts reduced the 4-nitro-l,8-naphthalic anhydride with the highest conversion rate （〉99%） and the highest ratio of hydro- xylamine to amine （95：5）. In contrast, the onion extracts reduced 4-nitro-l,8-naphthalic anhydride with a conversion rate of 94% and a ratio of hydroxylamine to amine of 8：92. The thiol-reducing agent, 13-mercaptoethanol, and metal cations, Ca2＋ and Mg2＋, greatly increased the reductive efficiency. This work provides an alternative strategy for biotransformation of nitro-polycyclic compounds.

Theoretical insights into the [4+2]/retro [4+2] cycloaddition approach to the synthesis of biaryls and polycyclic aromatics

A domino [4+2]/retro [4+2] cycloaddition process of cyclohexadienes with arylethynes or benzyne providing access to biaryls and polycyclic aromatics has been studied theoretically using density functional theory calculations. It has been found that the initial Diels-Alder (D-A) reaction acts as the rate-determining step and the consequent [4+2] cycloreversion reaction is feasible under the conditions used. Furthermore, the D-A reaction affects the regioselectivity, the origin of which is essentially derived from the good match of orbital coefficients between dienes and dienophiles as shown by using frontier molecular orbital (FMO) theory. Further investigation of the reactivity reveals that the reactions are predicted to fail to occur if an electron-donor group in the diene or an electron-acceptor group in the dienophile is lacking, as a consequence of the increased FMO energy gap. By further exploring the scope of substrates computationally, benzyne as an active dienophile was predicted to react with a variety of dienes in a cascade reaction under mild conditions with a low energy barrier, with the rate-determining step being the retro [4+2] cycloaddition.