室内燃烧源排放颗粒物及多环芳烃的粒径分布研究

室内燃烧源排放颗粒物及其多环芳烃(PAHs)的粒径分布是定量评估室内人群呼吸暴露风险的重要参数之一。该研究在再悬浮箱内模拟燃香、燃蚊香、艾灸和吸烟等过程,采用MOUDI采样器采集和分析颗粒物中17种PAHs;同时,采用颗粒物计数器,在实际房间中模拟艾灸和吸烟过程,得到室内颗粒物数浓度的衰减曲线。结果表明,燃烧源烟雾颗粒的排放因子为3.68～22.46 mg/g,颗粒质量粒径呈单峰型,峰值为0.25～0.44μm;US EPA 16种优控PAHs的排放因子为10.52～91.30μg/g,艾绒燃烧排放PAHs的粒径峰值为0.44～1.0μm,略大于其它燃烧源;1μm颗粒中PAHs的BaP等效毒性当量(BaP_(TEQ))的贡献占比为85%～98%。来源特征比值的研究显示,艾灸、燃香和吸烟释放的PAHs均归属于生物质燃烧类别。实际室内监测显示,在艾绒和香烟燃烧后室内颗粒物数浓度快速上升,在燃尽时达到峰值,而后在4 h内呈指数规律衰减,且0.3μm的细颗粒衰减最快。     

热解析-气相色谱或气相色谱-质谱法分析大气可吸入颗粒物中的半挥发性有机化合物

研制了一种热解析装置,并与气相色谱或气相色谱-质谱联用,定性定量分析了大气可吸入颗粒物中的半挥发性有机物。装置为直热式加热,升温速率快;直接安装在色谱进样器上方,无需冷阱聚焦。将热解析装置与气相色谱联用,优化了样品承载体材质、热解析条件和进样模式,并用于16种多环芳烃和9种正构烷烃的检测。结果表明,热解析-气相色谱方法对多环芳烃和正构烷烃的检出限分别为0.014~0.093 ng和0.016~0.026 ng,线性相关系数大于0.9975;用于3个城市PM10中的痕量多环芳烃和正构烷烃的定量测定,回收率分别在95%~135%(多环芳烃)和95%~115%(正构烷烃)之间。将热解析装置与气相色谱-质谱联用,比较了3个城市7种粒径分布的PMx(x=10,5,2,1,0.5,0.25,0.1)中的多环芳烃和正构烷烃,结果表明,不同粒径颗粒物均含有正构烷烃和PAHs,但含量相差很大。     

加速溶剂萃取法测定土壤和大气颗粒物中的多环芳烃和邻苯二甲酸酯

加速溶剂萃取法被越来越多地运用到环境有机污染物的分析。本文评价了一种平行加速溶剂萃取仪对分析土壤和大气颗粒物样品中多环芳烃(PAHs)和邻苯二甲酸酯(PAEs)的影响。研究结果显示，对于PAHs,加速溶剂萃取循环3次后加标回收率(67.3%～121%)几乎不再增加，而PAEs循环2次回收率即趋于稳定(65.7%～108%)。污染物的浓度与加标回收率的结果一致，PAHs和PAEs分别萃取3次和2次，分别占总浓度的98.4%和98.8%。在土壤和颗粒物中均显示出PAHs更难以提取，这可能与颗粒物和两类污染物的结合力有关。土壤样品量也是影响PAHs逐次提取效果的潜在因素；但萃取3次的总浓度结果相近，与样品量无关。样品量对PAEs的萃取效果影响不明显。加速溶剂萃取与索式提取的结果十分相近，部分PAHs前者的结果略好于后者。运用建立的方法分析了标准物质SRM-2585,也显示了该方法的准确性。     

控温超声提取-气相色谱-三重四级杆质谱测定大气细颗粒物(PM2.5)中的多环芳烃

建立了控温超声提取-气相色谱三重四级杆质谱测定大气细颗粒物(PM2.5)中多环芳烃(Polycyclic aromatic hydrocarbon,PAHs)的分析方法。PM2.5中的PAHs用二氯甲烷-正己烷(2∶1,V/V)控温超声提取3次,每次提取20 min,气相色谱-串联质谱分析,得到16种PAHs和6种替代物的标准曲线线性关系良好,相关系数均大于0.99,16种PAHs的检出限范围为0.013~0.12μg/L。实验中还观察到PAHs在空白滤膜中有微量存在,回收率实验中得到6种替代物的回收率在58.7%~108.2%之间,16种PAHs的空白滤膜加标的平均回收率在88.3%~104.0%之间,相对标准偏差均低于9.0%,实际滤膜加标的平均回收率在77.3%~98.7%之间,相对标准偏差均低于6.0%,本方法能够满足实际大气样品的测定。     

交通路口大气气溶胶的污染状况以及多环芳烃的污染特征研究

研究了城市交通路口大气气溶胶污染状况及气溶胶中多环芳烃(PAHs)的污染特征.在福州市主要交通路口之一的五四路和二环路的交叉路口采集大气中PM2.5、PM5、PM10、PM2.5~5.0、PM5~10、PM10~100及TSP.将优化的高效液相色谱编程荧光法用于各切割粒径气溶胶样品中的12种多环芳烃分析.研究结果表明:交通路口颗粒物中的飘尘(PM10)占总悬浮颗粒物(TSP)的70%;PM5占飘尘(PM10)的70%;而细粒子PM2.5占PM5的73%.交通源所产生的PAHs主要存在于细粒子PM2.5中,通过特征标志的多环芳烃的比值识别,交通路口大气颗粒物中的多环芳烃主要来源于机动车尾气排放.     

湖水中的颗粒物对水体生物膜吸附铅、镉的影响

采用逐级过滤的方式对湖水进行过滤,并用含有不同粒径颗粒物的湖水进行生物膜的培养,以研究水中颗粒物对生物膜吸附痕量重金属的影响.研究结果表明,生物膜上铁、锰氧化物含量与水中总铁、总锰含量呈明显的线性关系,锰氧化物的含量受水中颗粒物粒径分布的影响很大.生物膜吸附铅、镉的热力学过程符合Langmuir方程,且膜上铁、锰氧化物吸附铅、镉的能力随着湖水中颗粒物粒径的减小呈增强的趋势.     

微波消解-电感耦合等离子体质谱测定大气颗粒物中痕量稀土元素

研究了电感耦合等离子体质谱（ICP-MS）测定大气颗粒物中痕量稀土元素（REEs）的分析方法。在微波条件下,采用HNO3 ＋ H2O2（3 ＋ 1）混合介质能快速而有效地分解颗粒物样品。详细讨论了测定稀土元素的质谱干扰。通过分析不同粒径颗粒物中稀土元素的含量,初步探讨了大气颗粒物中稀土元素的分布规律。结果表明：颗粒物试样的粒径越小,稀土元素的含量越高。分析方法的检出限为0．7～2．8pg／mL,用于大气颗粒物国际标样（SRM 1648）中稀土元素分析,结果与推荐值有良好的一致性。     

固相微萃取-气相色谱串联质谱法检测北京大气细颗粒物中的多环芳烃

采用固相微萃取与气相色谱串联质谱联用,建立了快捷测定大气细颗粒物(PM2.5)中16种优控多环芳烃的方法.目标物先用二氯甲烷富集浓缩,然后用100 μm聚二甲基硅氧烷萃取纤维,通过超声萃取方式,在60℃条件下,萃取30 min.在优化的在多反应监测模式下,方法回收率在56.8％ ～ 106.0％之间,检出限为0.022～0.056 ng/m3.应用此方法检测了清华大学采样点采取的2013年1月1到15日北京PM2.5空气样品中的16种PAHs,实验结果表明,PAHs总质量浓度在290～1812 ng/m3之间,其中四环PAHs的总质量浓度最大(145 ～937 ng/m3),其次是五环PAHs(总质量浓度81.1～664.5 ng/m3),分子质量浓度较高的依次是荧蒽、芘、苯并(b)荧蒽、(蕴)、苯并(a)芘、苯并(k)荧蒽、苯并(a)蒽和菲,PAHs的污染主要来源于化石燃料燃烧和机动车排放.     

应用多元线性回归法测定黄河口不同粒径悬浮物中的有机碳含量

悬浮颗粒物(TSS)粒径与颗粒有机碳(POC)含量的关系研究,是河口淡、咸水混合过程中有机碳形态变化及其输送过程和输运通量研究的基础。在沉降法分级的基础上,结合激光粒度仪粒度测定,用多元线性回归分析法处理所得数据,校正了由于沉降分级的粒径交错现象而导致POC测定中小粒径TSS的POC含量偏低、大粒径TSS的POC含量偏高的问题,获得了样品中不同粒径TSS的POC含量。实验发现,黄河口水体中POC含量随TSS粒径的增加显著递减,80%以上的颗粒有机碳集中在<16μm的TSS中,而粒径<32μm的悬浮物承载了95%以上的颗粒有机碳的入海量。     

单一颗粒物扫描电镜能谱定量分析方法研究

采用实测标准样品、实际样品与模拟样品相结合的方法,对文献中报导的用于定量分析单一颗粒物化学组成的Casino和Quanta计算程序进行了考察和比较。计算结果表明,在校正颗粒物粒径效应时,Casino程序显示了良好效果。Quanta程序在计算沙尘颗粒物中常见的Na、Mg、A l、S i、P、S、K、Ca、Ti、Fe等元素含量时,取得和Casino程序基本一致结果。     

不同垃圾焚烧炉排放的PM10 中多环芳烃的研究

对大气可吸入颗粒物采样器进行改装，建立了垃圾焚烧炉烟气中PM10采样系统，并采集了三家垃圾发电厂焚烧炉排放烟气中的可吸入颗粒物。利用GC-MS对可吸入颗粒物中的16种多环芳烃进行定量研究，获得了多环芳烃的质量分数和浓度，并对不同环数的芳烃进行了比较，分析了不同样品中的多环芳烃的毒性参数。结果表明，颗粒物中的多环芳烃主要集中在4环、5环和6环，3环和2环所占比例较少；与燃煤电厂相比，垃圾焚烧发电厂排放的烟气中多环芳烃的浓度和毒性参数更高。     

Identification of polycyclic aromatic hydrocarbons (PAHs) in soil by constant energy synchronous fluorescence detection

In this paper, a novel method of constant energy synchronous fluorescence (CESF) was proposed to the simultaneous determination of different polycyclic aromatic hydrocarbons (PAHs) in a mixture of 16 components. When different appropriate intervals of the constant energy (Deltanu=1400 or 4800cm(-1)) were chosen during constant energy synchronous scanning, 13 PAHs could be identified and quantified by the corresponding synchronous spectra. Results show that their linear relations are fine and the limits of detection (LODs) were between 0.2 and 7.6ngml(-1). Then the application of CESF method proposed in the analysis of the real soil samples under the optimum conditions indicated that 11 PAHs could be identified and the total concentration of PAHs in a real soil sample is 5.1microg g(-1), most of PAHs in the soil samples had three or four rings. Recoveries of these PAHs were from 70.9 to 121.4% in most cases. This CESF method is a simple, rapid, sensitive method with high resolution and also suitable to analyze the complex mixtures of PAHs in other environmental samples.     

Odd-Even Effects on Transport Properties of Polycyclic Arene Molecular Devices with Decreasing Numbers of Benzene Rings

The electron transport properties of polycyclic aromatic hydrocarbons (PAHs) with different numbers of benzene rings tethered to narrow zigzag graphene nanoribbon (ZGNR) electrodes have been investigated. Results show that the transport properties of PAHs are dependent on whether the number of benzene rings in the width direction is odd or even. This effect is strong for narrow width PAHs, but its strength decreases as the width of the PAH is increased. PAHs with an odd number of rings exhibit poor transport properties, whereas the ones having an even number of rings show excellent transport properties coupled with a negative differential resistance (NDR) effect. Moreover, the linkage points and the structure of the molecules have a noticeable effect on the transport properties of the PAH, making the odd-even effect weaker or disappear entirely. Although the PAH with three benzene rings displays poor transport capabilities, it shows excellent rectification behavior compared to the other examined molecules. These studies present a feasible avenue for designing molecular devices with enhanced performance by the careful manipulation of the PAH molecular structure.     

Optimisation of supercritical fluid extraction of polynuclear aromatic hydrocarbons from spiked soil and marine sediment standard reference material

 For the determination of 16 PAHs in soils and sediment samples by GC/FID and GC/MS, the dynamic off-line supercritical fluid extraction with both pure and modified carbon dioxide has been evaluated. The optimisation of extraction parameters was performed for four individual groups of PAHs according to their number of aromatic rings (2–3 rings, 4 rings, 5 rings and 6 rings) by varying pressure (200–510 bar), temperature (50–150 °C), extraction fluid volume (10–50 ml), and the methanol modifier concentration (0–10%). Using a five level spherical factorial experimental design the number of experiments required for optimisation was 45. In spiked soil samples extraction efficiencies of 80–100% were achieved for the individual groups of PAHs. At the optimal set of conditions 10–30% lower recoveries of PAHs were obtained for the standard reference material NIST SRM 1941a (marine sediment). The largest differences between extraction recoveries of native and spiked PAHs occurred at high molecular weight PAHs. Using SFE efficiency data for the standard reference material, cluster analysis proved that dividing the 16 PAHs into four groups according to their number of aromatic rings was appropriate and correct. Received: 2 February 1996/Revised: 26 November 1996/Accepted: 30 November 1996     

HPLC determination of PAHs in mineral oils used as dispersing agents for herbicides

Summary The representative refined mineral oil samples, crude petroleum straightrun distillates, potentially used in the manufacture of crop protection products were analysed by isocratic and gradient high performance liquid chromatography (HPLC) to investigate their trace polycyclic aromatic hydrocarbon (PAH) content. Liquid-liquid extraction followed by size-exclusion column chromatography was employed to isolate the fraction containing PAHs with more than two fused rings. The identity of individual PAHs was confirmed by comparing their UV and fluorimetric detector signals with those recorded from reference standards. The level of extracted PAHs in the oil samples are discussed with respect to their physical and chemical properties.     

Assaying particle-bound polycyclic aromatic hydrocarbons from archived PM2.5 filters

Airborne particulate matter contains numerous organic species, including several polycyclic aromatic hydrocarbons (PAHs) that are known or suspected carcinogens. Existing methods for measuring airborne PAHs are complex and costly, primarily because they are designed to collect both gas-phase and particle-phase PAH constituents. Here, we report an assay for measuring particle-bound PAHs in archived filters from the network of U.S. monitoring stations for particles less than 2.5 microm in diameter (PM2.5), without the need for deploying specialized samplers. PAHs are extracted from Teflon filters with dichloromethane, concentrated, and measured at trace levels using gas chromatography-mass spectrometry. Although PAHs with 3-6 aromatic rings can be assayed, results are only unambiguously accurate for compounds with 5- or 6-rings, due to variable vaporization losses of the more volatile 3- and 4-ring compounds during sampling and/or storage. The method was evaluated for sensitivity, recovery, precision, and agreement of paired air samples, using PM2.5 samplers locally in Chapel Hill, NC. Additionally, three sets of archived samples were analyzed from a study of PM2.5 in the Czech Republic. Levels of some 4-ring and all 5- and 6-ring PAHs in both the local and Czech samples were consistent with published results from investigations employing PAH-specific air samplers. This work strongly suggests that assessment of particle-bound 5- and 6-ring PAHs from archived PM2.5 filters is quantitatively robust. The assay may also be useful for selected 4-ring compounds, notably chrysene and benzo(a)anthracene, if PM2.5 filters are stored under refrigeration.     

Strategies for the extraction of free and bound polycyclic aromatic hydrocarbons in run-off waters rich in organic matter

The objective of this study was to optimize and characterise extraction methods to examine the effects of wood ash application on polycyclic aromatic hydrocarbons (PAHs) concentrations in run-off waters for the evaluation of their distribution by storage in the different compartments (free and bound to dissolved organic matter, DOM), what influence their stability and persistence. The feasibility of solid phase extraction (SPE) and stir bar sorptive extraction (SBSE) for the determination of eight PAHs in run-off water samples has been evaluated. Both are appropriate to determine PAHs in run-off waters, but SPE is suitable for the determination of overall PAHs, while SBSE is used for the determination of free PAHs. The combination of both extraction techniques can then be used to estimate PAHs bound to DOM. Another approach based in the only use of SBSE is proposed for the estimation of all PAHs fractions (free, bound to DOM, and overall), once we are able to estimate the fraction percentage the free concentration represents. The percentage of free fraction was variable in the run-off waters with medium levels of DOM depending on the number of aromatic rings, molecular weight and water solubility of PAHs.     

Polycyclic aromatic hydrocarbons (PAHs) pollution recorded in annual rings of gingko (Gingko biloba L.): Determination of PAHs by GC/MS after accelerated solvent extraction

Retrospective monitoring of polycyclic aromatic hydrocarbons (PAHs) pollution levels was demonstrated by analyzing the annual rings of gingko (Gingko biloba L.) sampled from the Chengdu plain of southwest China. The samples of gingko trunk section, leaf, bark and its host soil were analyzed for PAHs by gas chromatography/mass spectrometry (GC/MS) after optimized accelerated solvent extraction (ASE). Compared to ultrasonic or soxhlet, ASE has high extraction efficiency thus meaningful contamination information contained in trunk tissue. The distribution of PAHs in gingko trunk, leaf and its host soil indicates that the main uptake pathway might be gaseous and particles-bound deposition via foliage with the exception of two-ring compounds from root, such as Nap and 2-methyl-Nap. PAHs in gingko trunk could be used to reveal the regional and historical contamination information, which is consistent with the environmental history of events (straw incineration) in Chengdu.     

Natural Attenuation and Biosurfactant-Stimulated Bioremediation of Estuarine Sediments Contaminated with Diesel Oil

We evaluated the bioremediation, by natural attenuation (NA) and by natural attenuation stimulated (SNA) using a rhamnolipid biosurfactant, of estuarine sediments contaminated with diesel oil. Sediment samples (30 cm) were put into 35 cm glass columns, and the concentrations of the 16 polycyclic aromatic hydrocarbons (PAHs) prioritized by the US Environmental Protection Agency were monitored for 111 days. Naphthalene percolated through the columns more than the other PAHs, and, in general, the concentrations of the lower molecular weight PAHs, consisting of two and three aromatic rings, changed during the first 45 days of treatment, whereas the concentrations of the higher molecular weight PAHs, consisting of four, five, and six rings, were more stable. The higher molecular weight PAHs became more available after 45 days, in the deeper parts of the columns (20–30 cm). Evidence of degradation was observed only for some compounds, such as pyrene, with a total removal efficiency of 82 and 78 % in the NA and SNA treatments, respectively, but without significant difference. In the case of total PAH removal, the efficiencies were significantly different of 82 and 67 %, respectively.     

Evaluation of polycyclic aromatic hydrocarbons in gasoline by HPLC and GC-MS

Summary In this paper the evaluation of polycyclic aromatic hydrocarbons (PAHs) in gasoline is described. A procedure involving a double extraction of samples with N-methylpirrolidone-water-phosphoric acid and with cyclohexane has been used followed by HPLC-DAD and GC-MS. The results obtained show that all gasoline samples contain PAHs with two to six rings and no substantial difference was noticed between leaded and unleaded gasoline. The benzo(a)-pyrene content ranged between 1.0–2.0 mg L⁻¹, a comparatively high concentration for a dangerous compound.