Development of analytical methods for polycyclic aromatic hydrocarbons (PAHs) in airborne particulates: A review

In the present work, the different sample collection, pretreatment and analytical methods for polycyclic aromatic hydrocarbons （PAHs） in airborne particulates is systematacially reviewed, and the applications of these pretreatment and analytical methods for PAHs are compared in detail. Some comments on the future expectation are also presented.

Highly Efficient Photocatalytic Remediation of Simulated Polycyclic Aromatic Hydrocarbons （PAHs） Contaminated Wastewater under Visible Light Irradiation by Graphene Oxide Enwrapped Ag3PO4 Composite

Effective removal of polycyclic aromatic hydrocarbons （PAHs） from wastewater before their discharge into the environment is an ever pressing requirement. In this study, for the first time, simulated PAHs contaminated wastewater was photocatalytically remediated with graphene oxide （GO） enwrapped silver phosphate as visible light-driven photocatalysts. The GO/Ag3PO4 photocatalysts exhibited superior photocatalytic activity and stability compared with pure Ag3PO4, g-C3N4 and TiO2 （P25）. The degradation efficiency of naphthalene, phenanthrene and pyrene could reach 49.7%, 100.0% and 77.9%, rspectively within 5 min irradiation. The apparent rate constants of photocatalytic degradation of 3 wt% GO/Ag3PO4 composRe photocatalyst were 0.14, 1.21 and 2.46 rain^-1 for naphthalene, phenanthrene and pyrene, respectively. They were about 1.8, 1.5 and 2.0 times higher than that of pure Ag3PO4, and much higher than that of g-C3N4 and TiO2. Meanwhile, the efficiencies of 44.6%, 95.2% and 83.8% were achieved for naphthalene, phenanthrene and pyrene degradation even after 5 times of recycling in the GO/Ag3POa-PAHs photocatalysis system. Reactive species of O2^- and h^＋ were considered as the main partici- pants for oxidizing naphthalene, phenanthrene and pyrene.

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.

Preliminary Study on PAHs Distribution in High-grade Oil Shale and Its Spontaneous Combustion Product in Fushun,Liaoning Province

Spontaneous combustion of oil shale is very common as a result of long-time exposure to the air in the Fushun West Open-Pit Mine and West Dump. The PAHs in the high-grade off shale and its spontaneous combustion product were analyzed semiquantitatively by GC-MS in order to investigate their distribution in different states and their potential negative effects on the environment. Totally 57 and 60 PAHs and their alkyl homologues were identified in the two analyzed samples, among which the alkyl derivatives were predominant, taking up to about 65% in the total PAHs. Those low-molecular mass PAHs （3- or 4-ring） were the main compounds in the two samples. Ten of sixteen USEPA priority pollutant PAHs were detected in two samples, of which phenanthrene was the richest whose contents were 6.93% and 15.03%. Based on comparison of analysis results, the amount and contents of PAHs, except for triaromatic steroid group, were higher in the burning oil shale. So it can be determined that the effects caused by spontaneous combustion of oil shale would be more serious and that the effects of the Fushun oil shale and its spontaneous combustion on the environment should not be ignored in the future work.

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.

PAH-biodegradation potential of indigenous microorganisms: evidence from the respiratory activity of surfacesediments in the Quanzhou Bay in China

Seven stations were established in the Quanzhou Bay （24.73°-24.96°N, 118.50°-118.70°E） in China on three cruises to determine the concentrations of polycyclic aromatic hydrocarbons （PAHs） and the numbers of PAH-degrading bacteria in surface sediments. Assessing the biodegradation potential of indigenous microorganisms by measuring the respiratory intensity with the addition of PAHs in sediment samples was also one of the aims of this study. The results show that the total PAH concentrations of the sediments were 99.23-345.53 ng/g dry weight （d.w.）, and the PAHs composition pattern in the sediments was dominated by phenanthrene, fluoranthene and pyrene. The numbers of phenanthrene, fluoranthene and pyrene-degrading bacteria during three cruises were 1.42×10^3-8.93×10^4 CFU/g d.w., 8.29×10^3 9.43×10^4 CFU/g d.w. and 7.05×10^3-9.43×10^4 CFU/g d.w., respectively. The addition of three model PAH compounds （phenanthrene, fluoranthene and pyrene） showed a great influence on the increasing of the microbial activity in the sediments. And there was a significant correlation among the change of respiratory activity, PAH concentration and the number of PAH-degrading bacteria. The change in respiratory activity under PAHs selective pressure could, to a certain extent, indicate the potential degradative activity of the PAH-degrading microbial community.

Phytoremediation of PAH-Contaminated Sediments by Potamogeton Crispus L. with Four Plant Densities

In order to investigate the effect of plant density ofPotamogeton crispus L. on the remediation of sedi- ments contaminated by polycyclic aromatic hydrocarbons, a 54-day experiment with four plant densities （642, 1 604, 2 567 and 3 530 plants/m^2） was conducted. The results showed higher plant density with slower plant growth rate. Surface area per plant was the most sensitive root parameter to plant density. At the end of the 54-day experi- ment, planting P. crispus enhanced the dissipation ratios of phenanthrene and pyrene in sediments by 6.5%-26,2% and 0.95%-13.6%, respectively. The dissipation increment increased with increasing plant density. Plant uptake accounted for only a small portion of the dissipation increments. Furthermore, P. crispus could evidently improve sediment redox potentials, and strong positive correlations between root surface area and the redox potential as well as between the redox potentials and the dissipation ratios of phenanthrene and pyrene were obtained, indicating that the oxygen released by the roots ofP. crispus might be the main mechanism by which P. crispus enhanced the dis- sipation of PAHs in sediments.

非道路用柴油机半挥发性有机物排放特性

在一台国Ⅱ标准的非道路用柴油机上对半挥发性有机物(SVOCs)进行采样研究发现,非道路用柴油机排放气相SVOCs高于颗粒固相SVOCs,且在两相中的排放量均呈现随负荷增加而增加的趋势.在气相和颗粒固相SVOCs中检出以烷烃为主,其次为多环芳烃类物质,包括2,3-二氢茚、四氢化萘、联苯、萘、芴、蒽、菲、芘等及其同系物.同时在对SVOCs中PAHs的研究中发现,柴油机排放的PAHs以气相为主,含量明显高于颗粒固相中PAHs;对比气固两相的浓度分布发现,气相PAHs中萘、苊烯、二氢苊、芴、菲、蒽为主,占气相PAHs质量比高达95%,而颗粒固相中PAHs则以菲、芘、荧蒽、屈、苯并(a)蒽等为主,其中苯并(a)蒽与屈在不同工况下质量比达80%以上;气相中PAHs环数以3环和2环为主,而大部分工况下颗粒固相中PAHs环数以4环为主,其次为3环.

Distribution and Risk Assessment of Polycyclic Aromatic Hydrocarbons in Mussels from the Middle and Lower Main Stream of Huaihe River

[ Object] The aim was to discuss the pollution status of polycyclic aromatic hydrocarbons （PAHs） in mussels from the middle and lower main stream of Huaihe River, which will provide a scientific basis for dietary safety of mussels. [ Method] Suspended matter, sediment, and mussel samples were collected from Wuxiaojie and Fushanji in middle and lower reaches of Huaihe River. All samples were extracted with Soxhlet, separated through Silica GeI-Al2O3 column, and determined by GC-MS, and then 16 typical PAHs contents in the prior table listed by American EPA were obtained. [ Result] The results indicated that total PAHs concentrations in suspended matters and sediments of Wuxiaojie were significantly higher than those in Fushanji respectively. However, PAHs concentrations in mussels of the two samplings showed little difference; as for single PAH component, low-ring PAHs were more advantaged in suspended matters of two sampling sites, while high-ring PAHs were more advantaged in mussels. PAHs in sediments of Wuxiaojie assumed low-ring aspect, though PAHs in sediments of Fushanji assumed high-ring aspect. [ Conclusion] In spite of that sediments and mussels were not yet contaminated according to the ecological risk assessment of PAHs, its potential hazards couldn＇t be ignored any more.

高效液相色谱法测定蓝绿藻中微囊藻毒素

以铜绿微囊藻为研究对象,考察了不同溶剂、不同超声波震荡时间和不同固相萃取(SPE)洗脱液浓度对藻毒素提取效率的影响,以及梯度淋洗HPLC分离藻毒素条件的优化。藻毒素浓度在1~100 mg·L-1范围内,峰面积与藻毒素进样量呈线性关系,相关系数为0.999 5,检出限为0.12 ng。方法可靠、灵敏度较高,用于实际藻样中藻毒素的测定,回收率为96.5%~98.0%。

Polycyclic aromatic hydrocarbons in soils of Beijing and Tianjin region: Vertical distribution, correlation with TOC and transport mechanism

The contents and distribution of 20 polycyclic aromatic hydrocarbons （PAHs） and heterocyclic aromatic hydrocarbons （HAHs） were investigated in 16 soil profiles of Beijing and Tianjin region. Transport of high molecular weight PAHs （HMWPAHs） and the correlation between total organic carbon （TOC） and their concentrations were also discussed. The results indicated that highly contaminated sites were located at urban or wastewater irrigation areas and pollutants mainly accumulated in topsoil （〈 40 cm）, with a sharp content decrease at the vertical boundary of 30-40 cm. Total PAHs/HAHs concentrations in soils from Tianjin were markedly greater than those from Beijing. Even the contents at bottoms of soil profiles in Tianjin were higher than those in topsoils of Beijing soil profile. HMWPAHs dominated the PAH profiles, exhibiting a uniform distribution of pyrogenic origin between topsoils and deep layers. Furthermore, the percentages of HMWPAHs remained relative constant with the depth of soil profiles, which were consistent with the distribution of particulate matter-associated PAHs in the local atmospheric environments. Therefore, HMWPAHs transport with particulates might be the predominant source found in soil profiles.

Binding characteristics of perylene, phenanthrene and anthracene to different DOM fractions from lake water

Six hydrophobic and hydrophilic fractions were isolated using XAD-8 and XAD-4 resins, and were extensively characterized. Partition coefficients of perylene, pbenanthrene and anthracene binding to the six fractions were determined by fluorescence quenching titration. The Kdo~ values obtained for the polycyclic aromatic hydrocarbons （PAHs） binding to the hydrophobic fractions were larger than those to the hydrophilic fractions. Nonlinear Stem-Volmer plots were observed when binding phenanthrene and anthracene to some hydrophilic fraction samples, suggesting saturation of polar interaction binding sites. A significant correlation of logKdo~ values with molecular weights and molar absorptivities at 280 nm was observed, while atomic ratio of C/t-I was found to be a poor indicator for aromaticity. Other structural descriptors such as paraffinic carbon and polarity influenced the DOM-fraction ability to bind PAHs. Different interaction mechanisms underlying binding of the different fractions to the PAHs were also discussed.

Emission characteristics of dioxins,furans and polycyclic aromatic hydrocarbons during fluidized-bed combustion of sewage sludge

Pre-dried sewage sludge with high sulfur content was combusted in an electrically heated lab-scale fluidized-bed incinerator. The emission characteristics of polychlorinated dibenzo-p-dioxins （PCDDs）, polychlorinated dibenzofurans （PCDFs） and polycyclic aromatic hydrocarbons （PAHs） were studied. Coal and calcium oxide （CaO） were added during the sewage sludge combustion tests to optimize combustion conditions and control SO2 emission. The results indicated that the flue gases emitted during mono-combustion of sewage sludge were characterized by relatively high concentrations of SO2, NOx and organic pollutants, due to the high sulfur, nitrogen, and volatile matter content of sewage sludge. The total 16 USEPA priority PAHs and 2,3,7,8-substituted PCDD/Fs produced from sewage sludge combustion were found to be 106.14 μg/m^3 and 8955.93 pg/m^3 in the flue gas, respectively. In the case of cocombustion with coal （msludge/mcoal =1：1）, the 16 PAHs and 2,3,7,8-substituted PCDD/Fs concentrations were markedly lower than those found during mono-combustion of sewage sludge. During co-combustion, a suppressant effect of CaO on PCDD/Fs formation was observed.

热处理对致密岩石物理性质的影响

致密气藏低孔低渗和超低含水饱和度等特征使其潜在水相圈闭损害严重,致密天然气产出表现为多尺度特征.选取泥页岩、致密砂岩和致密碳酸盐岩岩心,开展了100-600℃高温处理对岩心渗透率、孔隙度、重量、长度、直径和声速的影响实验.实验结果表明,碳酸盐岩、致密砂岩和泥页岩的热开裂阈值分别在300-400℃、300-500℃和500-600℃;高温处理后,岩心重量和密度降低,体积增加,泥页岩岩心孔隙度和渗透率提高幅度最显著,600℃处理后声波时差比常温时岩心声波时差提高了1.3倍.热处理消除了水相圈闭和粘土矿物膨胀损害,提高岩石孔隙度和渗透率,恢复或改善致密储层多尺度传质,有利于致密天然气资源开发,但同时高温使岩石破裂,扩展天然裂缝或产生新裂缝,导致工作液漏失,因此,热致裂给勘探开发致密天然气提出了机遇与挑战.

Polycyclic aromatic hydrocarbon biodegradation and extracellular enzyme secretion in agitated and stationary cultures of Phanerochaete chrysosporium

The extracellular enzyme secretion and biodegradation of polycyclic aromatic hydrocarbons （PAHs） were studied in agitated and shallow stationary liquid cultures of Phanerochaete chrysosporium. Veratryl alcohol and Tween80 were added to cultures as lignin peroxidase （LIP） and manganese peroxidase （MnP） inducer, respectively. Shallow stationary cultures were suitable for the production of enzyme, whereas agitated cultures enhanced overall biodegradation by facilitating interphase mass transfer of PAHs into aqueous phases. The use of a LiP stimulator, veratryl alcohol, did not increase PAH degradation but significantly enhanced LiP activity. In contrast, Tween80 increased both MnP secretion and PAH degradation in shallow stationary cultures. On the other hand, high PAH degradation was observed in agitated cultures in the absence of detectable LiP and MnP activities. The results suggested that extracellular peroxidase activities are not directly related to the PAH degradation, and the increased solubility rather than enzyme activity may be more important in the promotion of PAH degradation.

Distribution characteristics and ecological risk assessment of PAHs in surface waters of China

The concentrations of PAHs in the surface waters from seven river basins in China were summarized from literature published from 2000-2010. Subsequently, the risks from individual PAHs and Y. PAHs in the surface waters of China were quantified by comparing the overlap between the probability distributions of exposure concentrations with the probability distributions of toxicity data. The results show that the concentrations of 15 PAHs in the surface waters ranged from 3.09 to 38139.00 ng L-a, with a geometric mean of 474.93 ng L-1. The significantly higher concentrations of the 15 PAHs occurred in the surface waters from northern China when compared with those from southern China. The concentrations of the 15 PAHs in Chinese surface waters were higher than those in other waters worldwide. The MOSI0 （margin of safety） values were calculated at 90th percen- tile values of exposure concentrations and 10th percentile values of toxicity data, with 5.75, 0.17, 2.33, 0.30, 0.57, 1.74, 1.05, and 0.11 for Ace, Ant, Flu, BaP, Flua, Nap, Phe, and Pyr, respectively. The probabilities of the individual PAH concentrations exceeding the 10th percentile value of the toxicity data were 6.06%, 2.07%, 9.51%, and 2.07% for Nap, Ace, Phe, and Flu, re- spectively, suggesting minimal risk to aquatic organisms; however, the probabilities of BaP, Ant, Flua, and Pyr exceeding this value were 19.49%, 25.46%, 15.15%, and 30.50%, respectively, indicating potential risks. Among the individual PAHs, the ecological risk from Pyr was the highest, followed by, in descending order of risk, Ant, Bap, Flua, Phe, Nap, Flu, and Ace. Additionally, the combined ecological risk of ~ PAH8 in Chinese surface waters was significantly higher than any that of in- dividual PAHs alone. The MOS0 values in the river basins were 〈 1, except for the Haihe River Basin, suggesting a potential combined risk from E PAH8 in the other six fiver basins. The probabilities calculation indicate that low to high ecological risk from E PAH8 for all aquatic species was reported in the Liaohe River Basin （65.58%）, Huaihe River Basin （57.15%）, Songhua River Basin （46.49%）, Pearl River Basin （38.41%）, Yangtze River Basin （25.98%）, Yellow River Basin （15.92%）, and Haihe River Basin （5.22%）.

一种考虑虚拟质量力的两相压力波速经验模型

前人建立的两相压力波速经验模型未考虑虚拟质量力,本文考虑虚拟质量力、管壁弹性、管壁粗糙度等因素,通过求解双流体模型的小扰动,提出了一种新的气液两相压力波速经验模型.以一个具体的工程实例为背景,运用数值方法对其求解,得到的计算结果与前人实测的实验数据一致.结果表明,当空隙率较小时(0<Φ<15%)时,虚拟质量力对压力波速的影响不大,当空隙率较大时(Φ≥15%),考虑虚拟质量力计算的压力波速远大于不考虑虚拟质量力计算的压力波速.经验公式也可达到准确求解压力波速的目的.

Effect of organic wastes on the plant-microbe remediation for removal of aged PAHs in soils

The effectiveness of in-situ bioremediation of polycyclic aromatic hydrocarbons （PAHs） may be inhibited by low nutrients and organic carbon. To evaluate the effect of organic wastes on the PAHs removal efficiency of a plant-microbe remediation system, contaminated agricultural soils were amended with different dosages of sewage sludge （SS） and cattle manure （CM） in the presence of alfalfa （Medicago sativa L.） and PAHs-degraders （Bacillus sp. and Flavobacterium sp.）. The results indicated that the alfalfa mean biomasses varied from 0.56 to 2.23 g/pot in root dry weight and from 1.80 to 4.88 g/pot in shoot dry weight. Low dose amendments, with rates of SS at 0.1% and CM at 1%, had prominent effects on plant growth and soil PAHs degradation. After 60-day incubation, compared with about 5.6% in the control, 25.8% PAHs removal was observed for treatments in the presence of alfalfa and PAHs-degraders; furthermore, when amended with different dosages of SS and CM, the removed PAHs from soils increased by 35.5%--44.9% and 25.5%-42.3%, respectively. In particular, the degradation of high-molecular-weight PAHs was up to 42.4%. Dehydrogenase activities （DH） ranged between 0.41 and 1.83 ~tg triphenylformazan/（g dry soil.hr） and the numbers of PAHs-degrading microbes （PDM） ranged from 1.14x106 to 16.6x106 most-probable-number/g dry soil. Further investigation of the underlying microbial mechanism revealed that both DH and PDM were stimulated by the addition of organic wastes and significantly correlated with the removal ratio of PAHs. In conclusion, the effect of organic waste application on soil PAHs removal to a great extent is dependent on the interactional effect of nutrients and dissolved organic matter in organic waste and soil microorganisms.

Distribution and Source Apportionment of Polycyclic Aromatic Hydrocarbons from Atmospheric Particulate Matter PM2.5 in Beijing

A total of 11 PM2.5 samples were collected from October 2003 to October 2004 at 8 sampling sites in Beijing city. The PM2.5 concentrations are all above the PM2.5 pollution standard （65 μg m^-3） established by Environmental Protection Agency, USA （USEPA） in 1997 except for the Ming Tombs site. PM2.5 concentrations in winter are much higher than in summer. The 16 Polycyclic aromatic hydrocarbons （PAHs） listed as priority pollutants by USEPA in PM2.5 were completely identified and quantified by high performance liquid chromatography （HPLC） with variable wavelength detector （VWD） and fluorescence detector （FLD） employed. The PM2.5 concentrations indicate that the pollution situation is still serious in Beijing. The sum of 16 PAHs concentrations ranged from 22.17 to 5366 ng m^-3. The concentrations of the heavier molecular weight PAHs have a different pollution trend from the lower PAHs. Seasonal variations were mainly attributed to the difference in coal combustion emission and meteorological conditions. The source apportionment analysis suggests that PAHs from PM2.5 in Beijing city mainly come from coal combustion and vehicle exhaust emission. New measures about restricting coal combustion and vehicle exhaust must be established as soon as possible to improve the air pollution situation in Beijing city.

Organochlorine pesticides and polycyclic aromatic hydrocarbons in water and sediment of the Bosten Lake,Northwest China

We evaluated organic pollution in Bosten Lake, Xinjiang, China, by measuring the concentrations and distributions of organochlorine pesticides （OCPs） and polycyclic aromatic hydrocarbons （PAHs）. Water and sediment samples were collected from 19 sites 031-1319） in the lake for analysis. Our analytical results show that the concentrations of total OCPs in water ranges from 30.3 to 91.6 ng/L and the concentrations of PAHs ranges from undetectable （ND） to 368.7 ng/L. The concentrations of total OCPs in surface （i.e., lake bottom） sediment ranges from 6.9 to 16.7 ng/g and the concentrations of PAHs ranges from 25.2 to 491.0 ng/g. Hexachlorocyclohexanes （HCHs） and dichlorodiphenyltrichloroethanes （DDTs） account for large proportions of the OCPs. Low α- to γ-HCH ratios in both water and sediment samples indicate possible contributions from both industrial products and lindane. DDTs in water are probably from historical input, whereas DDTs in sediments are from both historical and recent inputs. Moreover, DDT products in both water and sediments were from multiple sources in the northwestern part of the lake（B11, B12, B13, and B14）. Fugacity ratios for DDT isomers （p,p＇-DDE and p,p＇-DDT） at these sites were generally higher than equilibrium values. These results suggest that the input from the Kaidu River and diffusion of DDTs from the sediment to the water are responsible for DDT pollution in the water. Lower-molecular-weight PAHs, which originate primarily from wood and coal combustion and petroleum sources, represent the major fraction of the PAHs in both water and sediment samples. Our findings indicate that OCPs and PAHs in Bosten Lake can be attributed primarily to human activities. A risk assessment of OCPs and PAHs in water and sediment from Bosten Lake, however, suggests that concentrations are not yet high enough to cause adverse biological effects on the aquatic ecosystem.